I purchased Portal 2 but accidently assigned the steam account to my sister's PSN account rather then mine. How, if possible, could I re-assign my steam account to my PSN account?
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Yes, you can.
you go to the ps3 account station and they will give you the password to your new account. sukka
At the settings menu for the PS3. PSN settings are set in the master account after you are connected and logged into the account
Depends what you want to do, you don't have to be online at all for the PS3 to work.
buy a new ps3