I have not used the PC-E 24mm for my own work, but Canon's counterpart the TS-E 24mm II on a 5D mark II. I recently decided to move to second-hand digital medium format though with a Linhof Techno to get a workflow more similar to 4x5".
I did mostly landscape with it and was very pleased with the results, if not shifting more than 6mm and using it at f/8-f/10 with the 21 megapixel sensor. The Canon has is better designed in the way that shift and tilt work independently.
If you need higher resolution than 20-22 megapixels I'm afraid that the 135 wide-angle options may be a bit disappointing though. It is one of the reason I got a MF system, to have better options on wide angles.
The live view is great in adjusting tilt and focusing, working with live view of the quality of the modern Canon and Nikon is in many aspects superior to ground glass I think, especially in dim lighting.
Here is one example image made with the TS-E 24 on the 5D mark II, f/8 with some tilt:
http://torger.dyndns.org/example-tse24.jpg
I made two exposures, the sky is exposed darker and then manually merged with the edge along the horizon, should not affect sharpness etc in the picture.
You can still see that there is some sharpness loss towards the edges. I'm starting to shoot more at f/10 now to get more even sharpness.
I guess you can shoot pretty much anything with the PC-E 24mm or TS-E 24mm as you can with a 90mm on your 4x5", but the quality resolution-wise is not really at the same level.
Here's another example:
http://torger.dyndns.org/example-tse24-2.jpg
note that the rather heavy vignetting is added in post-processing for artistic purposes. In this picture the camera was mounted above my head and the lens shifted down 6mm. This shot is also at f/8, but should have used f/11, stuff a bit too close and most notably the left tree is a bit out of focus. This is an example which I could not shoot with my Techno, having the camera mounted above my head requires live view on a screen to look at from a distance to be able to see anything and compose the image.
(note: at some point I will take down the images in the urls, don't like to have my images all over the internet)
As stated is previous post above with links to test charts the TS-E 24mmII is a bit sharper than the Nikon PC-E 24mm, so when sharpness limitations is seen on the 21 megapixel Canon sensor with the TS-E 24, it will certainly be more obvious on the 36 megapixel Nikon sensor with the PC-E 24. I owned a 7D too so I could test the TS-E 24mm performance with very small pixels (would correspond to 45 megapixels fullframe), center performance is then fine, but when shifted to correspond to an unshifted fullframe corner it does not look that good regardless of aperture. My conclusion was that 135 systems cannot really do high resolution corner-to-corner on wide angles with the current lenses. It shall be interesting to see more results from the D800 though.