My wife and I moved to Charlottesville from Baltimore last summer. We love it down here. There's tons to do: Shenandoah National Park, Wineries (dozens of them), the Downtown Mall, Breweries, Monticello, Luray Caverns is nearby, plenty of biking and hiking trails, summer festivals and farmer's markets, some decent artists come through here, too (Wilco, Willie Nelson, CSN, Aretha Franklin, Ron White, Dave Matthews of course).
There's an interesting mix of people here, too. While UVA and Downtown are relatively "cosmopolitan", it's pretty rural once you go 15 or 20 minutes in any direction. My wife and I live right on the border between the two. It makes for interesting trips to the grocery store and Target. You'll see an F350 truck with a Palin sticker literally parked right next to a BMW reminding you to Buy Fresh, Buy Local.
The pace of life is definitely slower here than it was in Baltimore. It took us a little while to adjust (I think we're still adjusting), but we're liking the slower pace more and more. People will actually take the time to talk to you when you're out and about.
With UVA here, there are lot of folks who have jobs affiliated with them, whether it's medical or academic-related. Martha Jefferson Hospital is another big employer in the area. The other big employer (which brought us here) is DoD. A lot of folks have moved here from Northern VA, DC, MD, and all over the country to work in DoD-related jobs over the past 3 or 4 years. As a result, there's quite a lot of development going on along 29, especially north of the city. We haven't figured out whether this is a good or bad thing yet.
What other kinds of advice/recommendations were you looking for?