Well there is defianately big usability differences, but it's all a matter of taste.
The only thing to realy keep in mind is that if your using mostly QT-based applications you'd probably want to stick with KDE. If your using mostly GTK-based applications then you'd probably want to stick with Gnome.
QT and GTK are what is known as 'toolkits'. These are library API sort of thing that provide the look and feel of applications. Programmers use them to make their jobs simplier and provide a more unified familar look to their programs. Things like menus, file dialogs, buttons, and such. Otherwise each programmer would have to make up his own widgets and everything would be ugly and different from app to app.
As long as you stick to one or the other Desktop Enviroment (DE) the UI is pretty unified and not much of a problem to deal with. Linux/KDE/Gnome gets the reputation for being a bit of a hog and some of that comes from when people mix and match between GTK and KDE applications.. Since then you'd have to load up and have running most of KDE plus most of Gnome it can be a lot to handle on slower machines.
So some things to look at when deciding (in no paticular order):
1. Do you use mostly GTK or QT apps?
For a typical QT application look at Konquerer. It's like Window's Explorer were it is dual natured File browser and Web browser.
http://www.konqueror.org/
For a typical GTK app look at Nautilus. It's just a file browser only with two different modes: a 'spatial' mode ala Mac OS and another mode (which takes a bit of editing to get default) that is a more familar windows-like mode.
http://www.gnome.org/projects/nautilus/
2. The Office Suites.
Gnome's Office suite is called 'Gnome Office'. It consists of different applications from different projects that are a bit throw together and given a similar look and feel. One is Abiword word editor. Another is Gnumeric, which is a spreadsheet program.
http://www.gnome.org/gnome-office/
KDE's is Koffice, which is a more unified project specificly designed to create a office suite. It consists of many programs, some of which offer functioanility and features beyond what is aviable with MS Office.
http://www.koffice.org/
And then the third option is OpenOffice.org. It's a rather bloated, but VERY full featured office suite that will provide the highest compatability (ui look and feel, applications, file format compatability) with MS Office. Designed to be a functional replacement. It's a GTK app and can integrate quite closely into Gnome.. but it will have a slightly different UI and depends on Java for full functionality.
http://www.openoffice.org/
3. Little games.
Both Gnome and KDE have their little games, like card games, tetris games, and such.
4. Look and feel.
Eye candy, themes, animations, visual toys and indicators.
Gnome is more about simple functionality. KDE has lots of little details that can be toned down if they aren't what you like.
They have various third party add-ons. Pagers on the taskbars, applets, toys. Gdesklets for Gnome and Karamba (and there maybe something else, too) for KDE are nice little do-dads to add things to to your desktop. Stuff like cpu indicators, and temp and fan monitors. RSS feed and news bulletin toys. Stuff like it.
Also theming is very important and customizability. For isntance Gnome's default look is quite pallid. What I do is delete the the bottom bar, and only use the top panel. On that I have my gnome menu, battery indicator applets, cpu/disk/memory graphical monitors, launchers for my favorite programs and a drop down menu in the upper left hand corner for selecting aviable windows (like Mac OS uses.. drop down window selector list). Then I select a nice SVG theme and make a fancy background.. as well changing some of the windowing behavor of metacity (my standards are pretty low).
KDE can get very fancy, too. More fancy probably.
(Some people say that KDE is most similar to Windows and may provide the easiest transition.)
You probably seen screenshots of 'desktop shell replacement' for Microsoft Windows that makes things fancy and gives weird menus and such. Multiply that buy a hundred and you get what you can get thru Linux and X windows.
Things can get very customized.
Other people like going the other way. They ditch the whole desktop enviroment bloat and go just with a very simplistic enviroment.
A poplular way to do this is just by using a Window manager and nothing else. A popular one is Fluxbox.
So basicly what you want to do is install both Gnome and KDE if you have the disk space aviable.
Then you just try one out for a while, then the other and play around with them.
On a side note:
As a user you only have access to your home directory. My home directory is /home/drag/
If you mess up or trigger bug you make screw up the enviroment for your user, but you can be sure that the rest of the system is safe from your experimentations. As a regular user it's fairly difficult to crash the the system or delete any files or goober up any configuration files to ruin everything.
However as root it's very very easy to screw everything up completely. With one command you can wipe out the entire OS before you get a chance to blink and it WILL NOT ask you y/n on many occasions.
So if you get to the point were your user account is messed up or you want to reset everything back to defaults you have two choices:
1. Create another user account and use that one instead.
or
2. Delete or move all your user setting configuration files, then everything will automaticly be set back to default settings when you log in.
To do #2 keep the following in mind:
One thing to keep in mind is that Linux doesn't have a registry like Windows does. For User-specific configurations they are stored in .filename and .directoryname files and directories in your home folder.
The . before the name makes the files 'hidden'. So you don't normally see them in your file managager or normal 'ls'.
If you open up a terminal and go:
ls -al | less
you can see all of these. If you ever reach a point were you completely screwed up your UI and want to go back to the default, you can simply delete them.
The command to do that is:
rm -r ~/.??*
or if you feel aggressive
rm -rf ~/.??*
!however that is not safe. Any information there will be lost forever! There is NO UNDELETE, so very carefull.
A better way is to move them out of the way.
mkdir ~/savedSettings
mv ~/.??* ~/savedSettings/
That way you move them out of the way. If you need information back out of them or you want to move them back then they are always in the savedSettings directory.
Note that ~/ is a shortcut that means 'your home directory'. For isntance my home directory is /home/drag/
going 'cd ~/` is the same as going 'cd /home/drag/'
? and * are wildcards. ? means 'any single alphanumeric character', and * means 'any number or no alphanumeric characters'.
Because if you go "rm .*" there are 2 special files, one is a simple dot (.) and the other is two dots (..) the single dot means 'this directory' and the two dots mean 'parent directory'.
So if I am at my home directory, /home/drag.. then..
. = /home/drag/
.. = /home/
It's just a shortcut.. but becarefull. there is no undelete. rm is very perminate. In fact the default file system zeros out the 'inode' numbers to make sure that no undelete will ever work well for security reasons.
So when I go:
mv ~/.??* ~/savedSettings/
I am basicly saying.. Move any file or directory with 2 or more characters in it's name AND beginning with a ., which is basicly every hidden file except . or .. since they only don't have enough characters to fill up the ?? stuff.
By doing this it makes it safe for you to mess around as much as you want. As long as you never do this stuff as root your always certain that no matter what you do you won't screw up anything other then your user's stuff. The rest of the system is safe from anything you do.. just as long as you never use root and be VERY carefull anytime it asks for your password or you use 'sudo' to become 'super user' (regular user with root abilities).
Hell it may be best if you want to experiment to have a second user setup so that you can keep your main user safe from any mistakes or bugs. Then when you find the very specific thing you want you can go back to your user and recreate it.
Also be sure that if your going to delete your user's settings to make sure that you backup your email and bookmarks and any other important information first, because often you will loose that information with your settings.