Hi all,
I have had this same issue with OS X Lion and it continued on to OS X Mountain Lion as well. I have had the wallpaper switching on me to the default solid blue color whenever I restarted (every month or so) and when switching between users (every other day or so). So this issue was very frustrating having to go back in and reset the wallpaper to my preference whenever I switched to either user. I found a solution that has been working for me for several restarts and several switching of users now:
First, I took some of your advice by locating all of my wallpapers into a 'Wallpaper' folder located in each user's 'Documents' directory. I copied to same wallpapers to each user so both user's have the same wallpapers to choose from.
Then, I installed the latest stable version of 'OnyX' (freeware software). I used OnyX on both user accounts to run through practically all the settings to clean up the entire Mac (Mac Mini, mid 2011) including: Verify [S.M.A.R.T. Status, Structure of volume, and Preferences], Maintenance [Permissions], Cleaning [System cache, User cache, Internet cache, Fonts cache, Log cache, Misc. cache]. I generally left the default checked boxes alone and didn't change any settings and Executed the program to run as default.
After running OnyX, I re-set my wallpapers for each user and went ahead and tested the restarting of the computer and switching back and forth between users. It was very easy to duplicate the bug previously, but now I could not get the wallpaper to switch back to the default blue as before. Everything seems stable with my wallpaper selection now.
Hope this helps someone. Thanks everyone for your input too.
As a side note, my Mac is running much smoother and quicker now too. =)