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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?
To create a Steam account you need to go the the Steam Powered website and go to Create A New Account. There will be a form to fill out and you'll get an email with a verification link that you need to click.
To get the free Steam gift vouchers, you will need to fill your Steam wallet with codes. When you get the right number of codes, you can redeem them for the free Steam gift vouchers.
DAG3000
No, once you purchased them you will have them after re-install process.Whatever you buy on your steam account stays with your steam account. You just need to log-in with your steam account and your dlc skins should be installed automatically to your computer.