If your PCI card uses a DLL and you install the DLL only when you install the card, you can check if the DLL file exists. On your diagram, from the File I/O palette, goto Advanced File Functions then select File/Directory Info. Wire File/Directory Info's path input to a path constant (or control) initialized to the path of the DLL file. If you get no error, the file is there and you can try to use it.
The DLL file should return an error if it couldn't communicate with the card. If you attempt to use the DLL and get an error, you could default to using the RS232 COM port and not the PCI card.