Vermont "Cities" of note:
Burlington: Home of the University of Vermont, and probably the only place to go if you want any sort of night life that doesn't involve country music.
Montpelier: This is more of a town. It's so small, it wouldn't even register on most maps if it wasn't also the capital of the state. On the other hand, it does have a few quaint shops, and is very liberal.
Barre: Montpelier's evil twin. Barre is inhabited partly by rednecks, and partly by nesting yuppies. Not worth visiting unless you enjoy country music.
Stowe: A yuppie's picture of what Vermont should be. Avoid the snapshot mountain town with expensive dining, but ski/snowboard here if you're into that sort of thing.
Rutland, Randolph, Springfield, etc: Generally considered too far south and too flat to really be part of Vermont. They try to be Stowe, but the mountains aren't nearly as good.