FYI, I'm in Mississauga and went to Sugarbush and Stowe last year, so similar situation to you.
If you take I-90 across New York then there are some nice photo ops, but not until you get towards Albany. Western New York on the I-90.....meh. As you get to the Vermont border there are some nice long views as well, Troy is a nice town along a hilly area.
The ride up Vermont to Sugarbush and Stowe is very nice, but you won't get many long vistas, mostly because of the mountains and trees will obscure things. Occasionally you'll get to a peak and may have a few chances.
Once you get into Stowe, there are plenty of great photo ops there. Across the river with the church steeple in view is a classic New England Norman Rockwell-like opportunity. Beautiful. Great examples of New England architecture in Stowe as well if you look just a little bit off the main road. Sugarbush doesn't have much around in terms of a town (blink and you miss it type thing), but there is some pretty countryside along the river outside Warren, VT.
Last year I took the 401 and then crossed at Ogdensburg. The bridge was EMPTY. Then you're in upstate New York and there's some great countryside out there. Across Lake Champlain and into Vermont, again very pretty. Was completely frozen over (we went in January) and took the kids out onto the frozen lake where people were ice fishing. Again, great pics.
Taking I-90 from Niagara Falls isn't quite as picturesque, and it's a bit longer than going the 401. But then again, the 401......I'm sure it sounds like you've been there, done that......just like us. So if you want something different, take I-90 right across NY and into VT.
Lastly, as for sunsets........tough call. The trees and mountains obscure "proper" sunset shots. The best you'll likely get will be the sun setting into the trees, with some decent light spilling across the mountains and/or valleys. Some wide angle shots might work. Long exposure night shots might work if it's clear outside. There's plenty of places to set up a tripod literally down the road from Sugarbush where you won't get ambient light and it's still near civilization so less concern about safety.