For an enthusiast there isn't much. If you are driving from Fl, I would stop by Fins. He is in Irmo, SC just outside of Columbia and has solid looking livestock and gets better quality stuff than most folks in the state that have a retail location (lots of people running stuff outta their garage or basement in NC/SC it seems.)
In Raleigh you have Reef Science and a few respectable LFS's. Nothing that will blow you away. I know there are a few other interent guys in the area other than Reef Science. Roe's is in Charlotte, Aquarium Specialty has a warehouse in Charlotte, but is based outta Columbia.
Can't think of anyone else at the moment...
Fintastic used to be worth the drive from Wilmington just to check it out, but when they moved they went way up on price (I know their rent must be insane where they are located now), I'm not crazy on their staff anymore either.
Salty's and Scales and Tails (I think that is the name) in the Huntersville area were OK. Had very nice owners, but not great selection.