That whole area you toured is beautiful. My wife and I did a very similar ride last spring, following a trail we thought might net us some interesting fossils, as well as some great, backroads adventures.
We drove down to Appalachia, Virginia and started a run through known coal territory, stopping anywhere there was an exposed seam and a place to park. There tend to be interesting fossils in the layers adjacent to, and even within coal seams. Also visited several dulcimer shops on the way.
We went through the mountains of southern West Virginia, crossed over into Kentucky at Great Bear Mountain (highest point in KY - also where I found a gorgeous fossilized connifer tip). We stopped at the KY Coal Mining Museum.
Later, we crossed into Tennessee through a national park, and spent a night in the Dollywood area. Then through to NC, through Cherokee, Asheville (already had visited Biltmore - it's as beautiful and fascinating as you say), and up to Statesville (visited my mom and brother).
Then back up north, stopping in an interesting town that Pat had read about in Maryland. We stopped to eat on the water at a restaurant, and sat next to the owners of a speedboat that ran on alcohol and kerosene - it used two Huey helicopter engines as power. We have pictures of that, as well as of the "Zippo car," which we had run into earlier in the trip. Yep, a car shaped like a cigarette lighter - only in North Carolina...
The scenery was all magnificent. As long as you didn't want to get anywhere fast, as it was all very windy mountain roads.