Hi,
All you have to make sure is that whether you have a secondary IP address on the external router interface (the interface facing the PIX outside interface) on the same subnet as the second pool of IPs that you are going to setup on the PIX, or that you add an static route (on the router), so you route all traffic destined to the second subnet to the PIX outside interface. The PIX Proxy-ARP feature would take care of the rest...
As you can see from the following link, the PIX does proxy-arping (or responds with its own MAC address, for ARP requests destined to another IP that is not its own) for any configured IP address on a global or static command. The Proxy-ARP feature is on by default, and you should never turn it off on the outside interface. Here is the link:
-- Command Reference (sysopt noproxyarp command):
http://cisco.com/univercd/cc/td/doc/product/iaabu/pix/pix_sw/v_63/cmdref/s.htm#wp1026942
So, bottom line, you just need to configure the nat/global statements (the normal way) and then make sure on the external routers that there is a route to the subnet specified on the 'global' statement. The route would be there by default if you configure a secondary IP address on the router's interface (and will show as directly connected), or you can enter an static route.
I hope this helps, and that I did not manage to confuse you :0)
Thanks,
Federico Rodriguez