I have mine set up to sync my iPhone and Dad's, both on my laptop.
How I did it, was to make him his own library in iTunes. On a windows machine, just hold the shift key and start up iTunes. Keep holding the shift key until you see this pop up:
Then I just made a library called "Dad's Iphone". Then just set it all up how you want it. You'll need to re-import the music and all from where it is now and set it up to look at the "Pictures" folder you want synced.
Keep in mind that you'll get the "This phone is synced with another library, blah blah blah" message and you'll have to erase and sync your wife's phone, so it will take it a while to redo it.
HOPEFULLY that will fix the problem. Not sure what is going on with yours.
Keep us posted. I'd be interested in finding out what the problem is with it.
Good luck, we're all counting on you!