The better way to ask the question is:
Can VGA be as good as DVI at (xxx) resolution?
The answer is generally: yes, it can, but you may have to put some effort (and money) into it.
DVI is an inexpensive, easy-to-use way to get a setup that is either good quality, or just won't work right at all. (I know, there are exceptions, but generally it is true). If you can do it, and don't want to make your life more difficult just for the challenge of it, go with the DVI.
VGA (at higher resolutions and refresh rates) is a complex, multi-signal analog RF system. If you just slap-in a $5 VGA cable and run 1600x1200@75Hz, you may well get poor image quality. I have a professional-grade CRT (whatever that means, it has better-than-average analog electronics) and there is a whole world of difference running into the D-Sub input with a generic cable vs. running into the BNC inputs with a multi-coax cable.
If you must use analog and are having a problem with image quality, first see if you can find a good VGA cable to borrow (maybe a CAD or Graphics Workstation at your work) and see if that makes it better. Keep in mind though, there is not a large market for 'good' VGA cables, particularly with D-Sub at both ends. It may cost more than upgrading to dual-dvi graphics card.
nBd