Look at the properties of the PCMCIA NIC. Verify that the "VMware Bridge Protocol" service is installed and enabled.
Run the Virtual Network Editor. Disable automatic bridging, then specify which physical NIC to bridge to the VMnet0 switch. Bridge the other one to one of the unused VMnet switches if you also want to use that one. If you want a guest to use the alternate NIC, change it's network mode from Bridged to Custom, and specify the appropriate VMnet switch.