How about making your doors out of straight mdf and routing a groove with a profile of your preference in from the edge about 2" all the way around to simulate a raised panel door?
When I built shelves for my shop out of plywood I plastered the edges with some "Bondo" car body panel filler and sanded after it cured in about 30 minutes. This gave a nice smooth sealed plywood edge that looked real nice after painting. I wouldn't use plywood for rails and stiles though.
On the same shelves I used kiln dried 2x4's and surfaced them with a jointer and planer to a common dimension making square corners. This looked a lot better painted than just undressed stud grade 2x4's and was a whole lot cheaper than buying "real wood". As well as using these dressed 2x4's for framing the shelves I also used them to build a frame glued and screwed to the bottom of each shelf. After filling the edges with bondo the plywood and 2x4 looked like one solid shelf. With the verticle support columns spaced 4 feet apart I have never had any problem with bowing even with my heaviest tools. The 3/4" C/D plywood even looks nicer than shop grade birch painted after a skim coat of bondo applied to the surface filling all the voids and grain followed by a real quick sanding with 100 grit. I can even climb on the shelves without a problem, something I wouldn't reccomend with laminated particle board shelves.
After 3 years of heave abuse I haven't had any chipping of the bondo. The high gloss white paint has also held up well and makes the shelves a lot brighter and easier to see stuff on.