Start by getting the right type of cable (pin connections), com port configuration, commands, and transmission control characters. This information should be available in the manual(s) for the equipment you want to communicate with. Finally, for example vi, check Serial Communication Examples under Search Examples in LabVIEW Help. You can also search this forum for additional information.
Before you develop your vi's, you can try out your commands and com settings with terminal emulator programs like HyperTerminal. If you have windows it should be under Communications in Accessories.