Well, it is not easy, but theoretically possible. I have never tried it, but it sounds plausible!
Now, the "recommended" way to do this is to set up the printers before a user profile is built on the machine, i.e. machines that the user has not logged into before. That is the trick of logging on as an Admin, adding the printers, then logging out. Next, you log in with a second administrator-level account, and replace the hidden Default User profile with the Administrator profile that you setup the printer maps to. Then, when the next user logs into that machine for the first time, they get the printer maps.
Since your user profiles already exist on the machines, then the above method is not for you. Now, there is another approach to take that should work for existing profiles. Technet article Q146050 talks about modifying the NTUSER.DAT file, which is where the HKEY_CURRENT_USER Registry hive exist. Each user profile has thei own NTUSER.DAT file, and that is where stuff like printer mappings exist. So, what you can do is login as Admin (with the printer mapping already established), open Regedit, and connect to the NTUSER.DAT file for each user profile on that box (so, you gotta do them one at a time); it is called Loading the Remote Hive.
At that point you "Modify the Default User subkeys as desired," which means you have to manually build the Registry branches and values that correspond to the proper Registry settings you want. You then Unload the Hive, close Regedit, log out, then have the user log in, and hopefully everything is working as you wanted!
Now, printers get stuffed in HKEY_CURRENT_USER\Printers
Take a look at the strucuture. There are subfolders for each installed printer you set up (local and network), plus some other folders. So, in the remote Hive, set up everything that you want the users to have. I would duplicate what is in your Admin profile into the remote Hive.
