Multiple IP addresses per NIC

Yes, it can be done in Windows:

1. Go to the Control Panel > Network Connections
2. Right click on the Local Area Connection (or whichever network connection you want to add the 2nd IP Address) and click Properties
3. Click on Internet Protocol (TCP/IP) in the connection box and click properties
4. Enter the first IP address in the properties box
5. Click Advanced
6. Click Add under the IP Addresses box and enter the information for the 2nd IP Address
7. Close all the boxes

Yes, it can be done.

On XP it was just a case of going into the "advanced" settings in the TCP/IP settings for the network.

I don't have Vista or any of the "server' variants of Windows to check against, but I'd be amazed if it wasn't possible.