This page will deal more with a trail which has a number of photographic spots for you. There are a number of waterfalls, some overlooks, and a couple of bridges to shoot here. You can count on spending about half a day here.
Begin by making a visit to the New River Gorge Visitor Center and from there follow the Fayette Station Road down into the gorge and the river. You will pass under the big bridge twice and there is photographic opportunity here, so be prepared. The road is narrow and one way and may be difficult to stop. Follow the road down into the gorge and just before you pass over the old bridge at river level, there is a parking area with room for about ten cars. You can stop here and walk out onto the bridge for photos and you will be able to shoot up at the the new bridge as well from here. You might catch some of the folks rafting and kayaking down the river as well, from here.
Continue across the bridge and wind on up the other side untill you come to a small parking area where there is a trailhead for Kay Moor trail.
At this point you have the opportunity to shoot three falls.
The first is Kaymoor Falls which is a short distance up the Kaymoor Mine trail and will fall directly on you feet as you walk up the trail. Can't miss this one.
The second one is not as obvious and is a bit more difficult to get to as the trail is a bit over grown, though not that hard to follow. Just bear to the right along the base of the mountain as you leave the trailhead. It's only several hundred yards up the creek, which will be on your left. Be careful here as the rocks are not so easy to navigate, but you'll find a nice cascade here and I think it is called Wolf Creek Falls.
Just back down the hill from the parking areas, is another of the Wolf Creek Falls. It's about 50 yards down the hill and you will have to scramble down into the creek. It's not the easiest scramble, but not that hard either. Just be careful.
Here is the Trails Newsletter from the National Park Service with trail descriptions and GPS etc. A good resource for hangin' in the gorge. I highly recommend you download a copy to your machine for safekeeping and convenience.
Fayette Station Road - After you have shot all the waterfalls at the Kaymoor trailhead, you will be driving out toward Fayetteville. You will come to a hard left curve in the road and there will be room to stop and there is an obvious overlook here. Good place for sunset. Further up the road and shortly thereafter, is Marr Branch Falls. (38.074552, -81.092733)
Endless Wall Trail - At about the halfway point on the trail you will begin to get views of the gorge and the bridge. Check the map I posted above and you will see Diamond Point. That's about the halfway point. If you are going for a sunset, then you will want to bring a flashlight or two and there is a spot before Diamond Point that may be good for you as well. At any rate, if you don't want to take the long way back to your car, the return the way you came, rather than completing the loop. Continuing the loop will be good for a morning hike and you will see vistas to the east that incorporate the endless wall as well.
Adventures on the Gorge - From "Smokey's on the Gorge" there is an observation deck that looks east and an open area on the lawn that looks west where people gather to watch the sunset, but you can's see the bridge from here, only from the deck and you probably need to be having dinner to get on the deck.