Hello sel57,
Do you mean you want to set what the in-use PSP is for certain LUNs or set the default that all will be assigned?
For individual LUNs:
kb.vmware.com/kb/1036189
kb.vmware.com/kb/2000552
For changing the Default(s):
kb.vmware.com/kb/1017760
(Note the 'Note' and 'Warning' at the bottom of this article and apply accordingly)
There are some good PowerCLI references for batch application on other posts:
communities.vmware.com/message/2332816
If a PSP is supported for use with that storage and what is running on it (e.g. MSCS has caveats kb.vmware.com/kb/1010041) then RDM or not, changing PSP should not cause issues.
Bob