You open Steam. When you see the window appear, look at the upper corner of the window where the '{yourIDhere}'s account' is written. Click on it and then select 'Change user...'. Click on the 'Logout' button.
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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.
I assume you already have an account then. If so, Steam should automatically log you in and keep you logged in everytime you turn on your computer as long as your internet connection is good to go. No internet = No Steam.
in the top right corner of the screen, click on "Account." Then, click on "Log out"
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?
Yes, you use your Battle.net account to log into World of Warcraft.