I've copied Linux from a floppy to a ancient laptop a long time ago. I don't remember all the details...
/dev/ folder is for special files... you can run a script that is usually suplied by the distro. Something like mkdevdir or something, but since gentoo uses the devfs demean all that stuff is handled automaticly...
If you just tar the / directory you are going to try to eat the /proc directory and that isn't going to work. Since the proc directory has virtual files holding the information of of proccesses you are going to try to copy a file that is monitoring the copy as it tries to copy itself... (It's not going to work)
The same may be true with the tmp, but that you don't have to worry about.
/etc/
So if you want to back up your entire OS, just make a tar ball of /boot /etc /home /lib /bin /sbin /root /usr /var the kernel if it wasn't already in /boot
Then to restore it you untar then into the root directory, make /tmp /proc /mnt/* /dev directories. Run the makedev script if you need to. Edit the /etc/fstab and /etc/lilo.conf or the /boot/grub stuff to match your new configuration if need be. Then re-run grub or lilo and you should be set.
You can probably do this all from your gentoo install cd.
I am not sure though if you need to do something extra for the /proc or /dev files... I think that it should figure it out on it's own, I am probably missing a couple other details. So you may want to test it out before if it's critical information.
However, that being said:
Most of the important stuff is you have /home folder (maybe /root, too, but it realy shouldn't be) and the /etc/ folder. All your user spefic setups and configs are in your home folder hidden in .folder files. (the . before the file name makes then normally hidden) And the /etc/ is for system wide configuration files. I'd personally just back those 2 up, because they probably take the most work for you to set up. If you didn't have all that much done in the /etc/ folder like setting up Apache with a special setup I wouldn't even back that up. The rest of the stuff can be regenerated automaticly on a reinstall. Then after you untar the install tarball and install that OS over again then download your /home tarball and untar it in the right spot. I do that when I install so I don't loose my information. Then you have to do the chown and chgroup stuff so that the files will be owned by you (your uid and guid numbers are the important information for file ownership, your login name is just for human convienance)
Just when you reinstall Gentoo and you made a backup of /etc/, make sure that you don't enable it to overright the /etc/ files automaticly if you untar it before the install!
ALso for niceties you can make a backup of all your downloaded and stored files you downloaded and installed in your /usr/portage/distfiles That's were all those tarballs you downloaded to install Gentoo are stored. If you back those up and then put them back in the same spot during the next install you don't have to re-download them. Out of a 6-gig install they probably take up close to 2 gig of that space. That way you can save a bit of load off of the mirrors, plus save yourself the time of re-downloading over a gig of information again.