Yeah this works, here is how i remember i did it when i followed a guide i can`t dig up. But it`s pretty simple:
#1 Set up VPN connection between the two locations (done)
#2 Download and install RendezvousProxy (Link below). Afaik it tricks your computer into thinking it is in the same subnet as the address you feed it.
http://ileech.sourceforge.net/index.php?content=RendezvousProxy-Download
#3 (Alternate solution) Download and install Zerospan (freeware) set up to do the above for you:
http://www.zerospan.org/
Disclaimer
I have no idea if doing what you want to do, or the method described above is in violation of any apple rules or distribution laws. I`d assume not, but you can never be too sure:)
edit: Also remember port configuration on your computer and router (if you use one) so it allows traffic on whatever port you chose. If you have a router you probably need to set up forwarding to the computer thats hosting the itunes library.
edit2: And if you don`t have a static ip where your itunes library is hosted, you could set up a deamon with www.dyndns.com so you don`t have to change the address manually every time your IP changes.
Btw, hope all of this helps. Keep us posted!