Well, the manuals are available here:
http://www.robot-forum.com/robotforum/manuals_software_and_tools_for_kuka_robots/krc2_manuals_for_kss_version_52-t229.0.html, and there's some example source code in the Serial manual. And if you search the forum, there are some other discussions about using serial on KRC controllers that cover a lot of the pitfalls and tricks.
As for code, browse to
kuka.skyefire.org and grab the serial.src and serial.dat files. That's some crude quick&dirty test code I threw together a while back. It's not pretty, but it worked.
Building an RS232 loopback tester also helps, and only costs about $5 in parts from Radio Shack. Get/build a null-modem adapter too. Telnetting from the WIndows side of the controller into the VxWorks side (run "telnet95 192.0.1.1") will let you watch what the robot
thinks it's sending/receiving, down at the hardware-driver level -- seeing that can help you nail down errors in your code.