This page will deal more with a drive through the gorge, which will present a number of photographic opportunities for you. There are a number of waterfalls, some overlooks, and a couple of bridges on this route. 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 Fayette Station Road down into the gorge and across the river. You will pass under the New River Gorge Bridge twice and there is photographic opportunity here, so be prepared, but the road is narrow and one way and it may be difficult to stop. This is "structural artwork - the longest steel span in the western hemisphere and the third highest in the United States.". You can read about it here, but I recommend stopping at the visitor's center before you venture down into the gorge, to get the full picture. One curious note is that this bridge has never been painted. Special kind of steel keeps it looking as it does.
Follow the road down into the gorge. 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 Fayette Station Bridge for photos. You will be able to shoot upward at the the New River Bridge as well from here. You might catch some folks rafting and kayaking down the river as well.
Continue across the bridge and wind your way up the other side. You will come to a bridge that crosses Wolf Creek. It's in a hard right hand curve and there is a service road just on the right after you cross where you can pull in and park, because there is a waterfall at the bridge. Small but pretty and interesting site.
Get back on Fayette Station Rd. and continue uphill untill you come to a small parking area at another right hand switchback. This is Wolf Creek and the trailhead for Kay Moor trail. Parking is tight and restrictive.
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. It falls at your feet trailside, just a short distance after crossing the foot bridge over Wolf Creek.
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 behind the trailhead sign as you leave the roadside. It's only several 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.
Just back down the hill from the parking area is another of the Wolf Creek Falls. It's about 50 yards back down the road from the parking and you will have to scramble down into the creek. It's not the easiest scramble through rhododendrun, but not that hard either. It's steep, but lots to hold onto. You can tell where others have been down here. 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.