I camped along Skyline and Blue Ridge Parkway last month--so beautiful! Raccoons took my trail mix though, almost figured out the latches on the Givi Cases...
Bring yer long underwear and glove liners, and raingear of course.
Skyland looked like a pretty cool and well-situated place to stay, but didn't see any of the rooms. Skyline, like the BRP, runs along the top of the ridge, so any road going up or down off it is likely to be fun and twisty as hell, from my sampling.