Take a look at the build journal I have for our "Little Tow" that I'm building:
http://webpages.charter.net/outtahand/littletow/index.htm
I have used expanding from (Great Stuff brand mostly) a LOT in the build. I used it for insulation in the roof and for insulation and extra rigidity in the nose of the trailer. I found it to work pretty good.
Yes, it does continue to expand for a while. You'll see pictures of this in my build journal. In trying to build panels as you described, you'll need to put in a couple "emergency escape" holes for the pressure to bleed off.
Other than the expansion issue, I think it would be a great way to build.
A couple notes on its use that have been mentioned, but I thought I would expand upon:
1) If you get any on your clothes, the clothes are done. It will NOT come out. Period. Wear lousy work clothes that you don't care about.
2) If you get it on other things that are porous, you'll have a heckuva time getting it off. Best to wait until it dries and hope that it didn't attach itself too hard.
3) Once you start a can, use it to the end. If the stuff hardens in the little delivery tube, that tube is done. You won't have a good way to use the rest of the can.
4) Buy a can or two more than you think you'll need. If you take a look at the Cost Log on my build journal, you'll see several places where I had to buy the Stuff. Although it expands, it will probably take more than you think.
5) Before you put in the foam, remember to think about whether you may need to run wires or anything else through that area. Once the foam is in, you won't run wires. If there's even a chance you might need to wire through the area, either put in a piece of pvc pipe or conduit to run the wires through after you've "foamed" it, or just put in some wires with the ends exposed just in case you need them later.