I've used the NI serial library and both NI and third party serial hardware and I've never seen a "hardware error" reported either.
My experience is that you have to grind through cable and connector issues, and independently verify that you have things right with the cable.
The single biggest issue is knowing if your devices are configured as DTE or DCE, as that dictates connector pinout and that in turn dictates cable wiring.
Once you know the cabling is OK, you need to check com port configuration on both ends. Data width, bit rate, stop bits, parity must all agree. You can always use and extra stop bit on the sending end in case the receiving port is having trouble with frame to frame timing.
Substituting one end or the other with a PC running Hyperterminal, or TerraTerminal, or Terminal (my current favorite) can also help you gain insight as to what's happening.
Worst case you can hook up a logic analyzer and look at everything at the signal level. I use to have an old Biomation K100D with an rs-232 probe that I hauled all over the world for the worst problems. Seems like overkill but it often served as my "final answer".
You can simplify your connection scenario while you figure out cabling / config issues - use short cable runs, lower the bit rate, etc.
Sometimes cable length and ground loop issues will hose up a connection even though you're kosher as far as cable wiring and config. NI makes opto-isolated serial ports to manage the ground loop problem. Work out your cable wiring and port config issues with the simplest possible connection scenario first if you're still having trouble.
Menchar