I've tried putting
!Run "pathtoexe\program.exe"
!Run ["pathtoexe\program.exe"]
!execute same as two above.

into my Theme.rc and step.rc. I still cannot get an external program to launch when litestep fires up.. what am I doing wrong?

thats because you can not just put bangs in your step.rc. !Run just opens the run dialog anyways so it won't do you much good. What you need to do is put them in your startup folder like you normally would or use mzscript's *script start proceedure.

just answered it here http://www.litestep.net/?section=4&action=details&catId=1&id=3448