as far as i can tell they don't use pc based controller which means your VB application cannot run on robot itself.
communication choice will depend on number of things but most important one is bandwith or speed. if it is limited,
you have to look for alternative comm method. RS232 is dead simple and it is so easy to do in VB. sounds like perfect choice
if the speed is not an issue.
you should start by looking at port specs (how fast can it go, what are the port settings, what is the protocol,
what is pinout, is it standard or something weird, you probably need crossover cable, handshaking is another matter...).
if you can find that out, job is almost done.