One place to start is in the LV examples. There you will find several examples for talking to the serial ports. Just keep in mind that serial communications is the least standard of all types of instrument IO, so if there is any other way in the world to talk to your target device, it's a good idea to use it.
Of course, on the other hand, if you can find a GPIB driver for the instrument, sometimes all you have to do to convert it to a serial driver is change the VISA resource the driver is talking to.
Keep us posted. If you have any specific issues come up, hollar. BTW: what are you wanting to talk to?
Mike...