We clearly need more information on how the card is configured. What is the OS?
Is this just a network card with multiple interfaces? Is each interface connected to a different subnet? In this case the routing tables will determine which interface needs to be used for any given outgoing connection. For any given destination IP, only one interface is appropriate in this case.
If multiple interfaces are on the same subet, there must be something to configure things e.g. for policy based routing, load balancing, or similar. The LabVIEW application shouldn'd need to worry about these things.