DISCLAIMER
It is almost never a good idea to update an SAP standard table directly. If you are new to SAP you can remove the "almost" from that statement.
So while I will answer your question I would strongly suggest that you try to find a SAP-approved way to update the necessary fields using BDC, BAPI or a released function module.
The following code will update all entries where exit_prnt_layout is blank:
update hrp5021 set exit_prnt_layout = 'STANDARD'
where exit_prnt_layout = space.
write:/ sy-dbcnt ' entries updated'.
And the same for exit_web_layout:
update hrp5021 set exit_web_layout = 'STANDARD'
where exit_web_layout = space.
write:/ sy-dbcnt ' entries updated'.