I love Brattleboro, VT, in the southeast part of the state. It's a nice little town with lots of artists and crafters and it's right along a river. If you're in the area, a couple miles west of downtown is Solinglass where you can watch a woman make blown glass; it's really interesting and it's free. The one caveat is that everything I saw said it opened at 9AM, but it doesn't open until 10. About a mile east of Solinglass is the Grafton Village Cheese Company which is mostly a shop selling cheese, jams, hummus and the like, and they also have a little viewing area where you can watch them make cheese. Not as cool as glass blowing, but still pretty interesting. And right next door to that is the Retreat Farm where they have a barn with various animals that's fun to walk through (cost was just a few dollars, can't remember exactly). The three things above would make a good morning or afternoon, and then maybe half a day in town looking around (I'm not a big shopper/browser myself).
If you end up in Keene, NH, go to the Horatio Colony House/Museum. I won't be able to adequately describe why it was so interesting, but really, go. The woman giving the tour new everything about every single item in the house and painted a good picture of what it was like to live at various times in the past. I know you didn't mention NH, but since it's between Vermont and Maine I figured you might drive through it. Keene isn't quaint like Brattleboro, but it's an interesting place to visit, too.