I usually spend some time fish Cataloochee each fall (during the elk rut). We usually stay in the campground and that is definitely the best way to access the most water. Unless you just insist on a backcountry site, I highly recomend the campground, it is relatively small and usually pretty quiet. Also Caldwell Fork runs into Cataloochee right there at the campground. I don't fish Cataloochee very often in the spring (just can't stay away from Abrams that time of year), but my experience is that is just doesn't fish as well as it looks like it should (and no, I'm not just saying that to keep people away). But, honestly I have had more hard days of fishing with little to show for it in that creek than any other in the park. But note, I keep going back, I do love that place. I think that one of the reasons Cataloochee may fish a little tougher than some of the park streams is that it may have a little higher concentration of brown trout that most streams (just my opinion). The creek fishes fairly well from the campground up to the confluence of Rough Fork and Palmer Creek. Given a choice between those 2 steams I will take Palmer every time and usually spend some time fishing it when I am there, my personal best brookie (a 9-10" beauty in late September) came from Palmer just below where Pretty Hollow comes in. Pretty Hollow fishes well as does Palmer all the way up to Lost Bottom - colorful names. I would definitely spend some time going up Palmer (watch out for bears and Rattlesnakes!), the fish are much more willing to smack a dry than they are in Cataloochee.
Coming back down from the campground, Cataloochee fishes well down to the bridge just above the group camping sites. From that bridge down to the group sites is again some of the best looking water I have ever seen, but it just doesn't seem to fish very well. This past fall I fished from the next bridge down, Asbury Crossing, back up the group sites and again that is some pretty water as is the water at Asbury Crossing. I have not been very far below Asbury Crossing and I have never fished Little Cataloochee which enters just below there.
All of this water is very easy to access from the Campground. And I have found that the fishing right beside the road can be pretty productive. I particularly like the stretch of water that runs behind the fields up to the little Methodist Church.