Speaking in broad stereotypes for ease of description, VT can be more hippie, more politically liberal, more green (multiple meanings intended), and just overall "more chill," which I prefer. The "live and let live" kind of folks.

There are pockets of VT that are primarily tourist focused (Killington, Jay Peak) and that can certainly affect a local vibe. And as with anywhere, there are small minded residents too. In highschool, I remember the "take back VT" people who were against same sex marriage and weren't quiet about it.

NH is definitely a purple state, politically. Indigent towns next to wealthy ones. More industrialized in the southeastern area. Less easy to stereotype as a whole, but lots of "live free or die" folks, both in their own red or blue ways. Red governor and blue senator are a nice balance imo (putting personal opinions aside)

Western NH feels like VT, southern NH feels like MA. Northern NH is more like ME. All within a three hour drive.

Source: lived in VT, NH, and ME for 30 years.