The best distillery tour is Jack Daniels in Lynchburg. Very comprehensive and a good lesson in the distilling process. The distilleries around the Smokies are small Moonshine distillers and basically just tanks to see, same as a micro brewery really. Moonshine is just unaged whiskey. Lots of flavors made today and still worth a visit though. Campgrounds inside the NP are dry, no hook-ups so as said above, do you want to stay closer to Pigeon Forge/Gatlinburg or Townsend and the quieter side? Townsend has a couple of nice private campgrounds.
As far as must see's there is Forbiden Cavern, Bush Beans factory that has a cafe for a good lunch and museum for their history. Its small and an easy go through. Townsend area has the Great Smoky Mtns Herritage Center and small railroad/lumber museum. The touristy things to do in town are still worth a visit. Lots of good shows and restaurants in the area.