For trails to wander start here:

Rules and regs, google George Washington & Jefferson National Forests (the link was too big to paste in); for hunting rules and regs I'd start with the State of Virginia's website, or at the archery range on base (I don't hunt, but I bet they know).

Blue Ridge Mountain Sports and Wild River Outfitters are reliable shops. Rei in Richmond is a good competitor worth looking at if you are buying gear. However, I've gotten the best backpacking trip advice from Blue Ridge Mountain sports over in the Hilltop shopping center (over on Laskin) or from their sister store in Hampton.

AT is out by Stauton on 64; you can get out into sections w/in the National Forests in 3-5 hours.