>>297568VA has glorious SNP and GWNF.
Westbygod (west virginia for you foreigners) has some really superb places (And to be totally honest, more stretches of boundless wilderness) but I'm always uneasy about anything but trails in WVA (to some extent) because there's alot of cabins and shit out in the woods to come up on.
Penn. is cool, I drive through it frequently but never been /out/ in it. Looks like a good place to get lost in the woods, but probably with the same problems of WVA.
There's a reason they call Virginia the Gem of the South OP.
Check out the AT, SNP and GWNF for some good distance hiking if that's your game. Check out Harpers Ferry (it's technically wva but it's the tri-state area of VA, WVA, and MD)
You get 1 epic cliff (east coast standards), a quaint little town that runs up a cliff with lots of cool rock formations (harper's ferry) and across on my side is Loudoun Heights, a cool ass mountain that drops off to the Potomac leaving an awesome face with lots of rocks.
Pic related, this is looking Eastward from the Loudoun side of the river.