My toughts...
GENERAL GUIDANCE: All roads except interstates in VT/NH are incredibly twisty and windy, which means if either of them is prone to car sickness, watch out. Also, everything takes about 2x to get to as the pure distance would suggest. It's like magic... it just takes forever to get there. You get used to it. And I really do recommend staying off interstates unless they HAVE to take them. The goodness is tucked away in the teeny little hamlets on rural state highways. You miss it on the interstates. Antoher thing to take note of is all the damage from Hurricane Irene. Roads are all obviously fine again, but if they look, they can see damaged houses, cars bent around trees, and high water marks 10-20 feet up the sides of buildings. That shit hit Vermont, like, Cormac MacCarthy-hard, and it barely made news.
IN VERMONT...
1. "Quaint Townery." I would say Woodstock VT (note that there's a Woodstock in every state up here, so don't confuse it with Todd's NH rec, I've never been there) is the cutest fucking place I've ever been, more or less. Rockefellers built it up with $ way back when, so it's all stone bridges, underground power lines, massive stone public library, cute shops, etc. If they stayed at a BnB anywhere in Woodstock, they'd be in for a treat. Really everywhere in Vermont is stunning and quiet. Only in a few places does it get anything like "traffic" or "congestion." It's mostly just fucking incredible, empty, and green. I would avoid the ski town areas (Stowe, Killington, etc) if they want real quaint stuff. Ski towns tend to have a lot of cheesy pizza / sub shop bullshit, and 80's condos and hotels.
2. "DA BEERS." If they're the kind of people who will enthusiastically wait in a long line for "holy grail" beers to take with them, then by all means have them go to Hill. Otherwise, if they're regular beer-loving mortals, Prohibition Pig is 1000x easier / more pleasant. The food there is fucking incredible, and the beer selection is a non-stop holy shit ride through new england's greatest hits. They almost always have Heady on tap, and several Hills. But they also have Lawson's, and Fiddlehead, and several other fucking goooooooooooooood beers that haven't become Internet Famous yet. And as Shiv said, around the corner are at least 2, maybe 3, beer shops that sell Heady and others. Also Pro Pig has built their own brewery on premises, and it should be serving by then I think. So Waterbury is a VT MUST. As for NH, I've never had anything but "solid locals" out of most of that state except down on the coast. Beer is Vermont's thing. OH -- and I do have one hidden little gem I found. In the tiny tiny town of Waitsfield VT, there's a REALLY good burrito place who also serves Heady / Lawsons / etc called "The Mad Taco." It's a walk-up counter, a tiny amount of indoor seating, and outdoor patio style seating out front. Town square is across the street, and everything's cute as fuck.
LODGING...
I have one secret spot that might or might not fit their bill. It's tucked back on a series of long dirt roads, in the middle of the Green Mountain National Forest, so the only activities are whatever the rustic old hotel offers (tennis, pool?), and hiking around. But it doesn't get any quieter or prettier. It's called the
Landgrove Inn. Neuro and I walked in once while motorcycling past just to see the inside. We always admire it on the way to my top-secret motocamping sites, which are reached via that same road on the east side. So if they want one of those "unplug / tune out / nature" overnights, but they don't want to camp, this place would rule. It's fucking ancient, and you can tell when you walk in. Ceilings are all like 6'6", everything creaks just a little, and it just oozes history.
NEW HAMPSHIRE... The thing about NH is that (as Shiv said) its goodness is tightly concentrated in the northern 1/3, and there are no secrets. Pretty much everyone else knows where to go, too. I will say that, again, if they're at all hikey people, then there's a spot we stayed that I'd STRONGLY recommend, called the AMC Highland Center at Crawford Notch, and it's run by the Appalachian Mountain Club. You can get private rooms for couples, but expect cozy-yet-spartan decor... it's really designed for hikers. The advantage of that place is that it is ON several of the most awesome hiking trails in NE, so you can walk out the door and have either hiking, biking, or kayaking adventures incredibly easily.