In virtual PC go to Edit -> Settings -> Networking
Make sure that the network card that is installed in your XP Pro 64bit is selected under Adapter1.
Then make sure your (XP Pro32bit) virtual pc's computer name is different to the XP Pro64bit computer name.
Setup TCP/IP in the Local Area Connection in the virtual PC. The IP address of the PC and the Virtual PC must be in the same range. The gateway and the DNS must be the same (This is if you use static IP addresses for your LAN)
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