There are several options for routing.
The obvious (and probably quickest) but boring and toll-laden route is I-90 to I-290 to I-495. Things to see and do along this route include watching semi trucks, paying tolls, and admiring rest area architecture.
Another reasonable route is to take I-90 to Fultonville/Fonda (exit 28), and then NY 30A to NY29 to Saratoga Springs. From there, I-87 north to exit 20, and NY 149 to US4 across Vermont until you get to I-89. I-89 to Concord, I-93 north a bit to I-393, and then rejoin US4. (You could of course also stay on US4 the whole way, rather than taking the interstates to Concord.) This takes one through the Lake George outlet store zone, slow driving but only for a short distance. Quechee Gorge (near White River Junction) is perhaps worth a stop, along with the nearby VINS nature center. Woodstock can also be a fun, if somewhat touristy, town.
A third reasonable route is to take NY 7 from the Albany area, to VT 9 across Vermont, which magically becomes NH 9 at the border. You could either follow NH 9 all the way to Portsmouth, or catch NH 101 at Keene to go towards Hampton Beach. This goes near the Bennington Battle Monument, which on a clear day offers an impressive view from the top. There's also the Bennington Museum which is probably best known for its collection of Grandma Moses paintings.
If going south along the coast from Acadia is an option rather than north to it, I'd suggest considering NY 360 to NY-8 to NY 9N, across the bridge to VT 17, and then VT 22A north to US 7. In South Burlington, the I-189 spur to I-89 to US-2 at Montpelier and that all the way to Bangor. Note that there are some significant hills on this route, particularly through the Adirondacks; the worst are probably on NY 8 between I-87 and NY 9N, where it's relatively steep and long and curvy. I've driven that stretch in my motorhome a few times without trouble, so it's not as though one's toying with death or anything, but some people aren't too comfortable with those sorts of driving conditions. (Downshifting and using engine braking are definitely called for.) It may look tempting to take VT-17 across to VT-100; you probably don't want to do that as the road over the Appalachian Gap between 116 and 100 is very steep and very curvy (and, I must say, quite beautiful). Along or near this route are the Shelburne Museum (very large and very eclectic), the Vermont Teddy Bear factory, Ben & Jerry's, the Fairbanks Museum in St Johnsbury (natural history mostly, but also a sort of meta-museum of how museums used to look) and an impressive little art gallery in the Athenaeum (public library). With a little extra time, once could duck down (or perhaps I should say up) into the White Mountains of New Hampshire; the Kancamagus Highway is one possibility there, among many.
