Some people say DVI is more clear. I have tried both in my LCD and can't tell any difference personally. The only difference I can tell is when you're not running at the native resolution. Using VGA, your monitor will need to be manually adjusted(or go though the auto adjustment) With DVI, the resolution is always the correct size on the screen. No gaps, nothing hanging off, etc etc.
I can't see DVI being that much different from VGA because the converter is basically a direct conversion.