To open to instances of Google Talk, first make a shortcut of googletalk.exe to wherever, I assume you have one your desktop you use.
So you Right-Click >> Properties, then under the "Shortcut" tab, in "Target" put this:"C:\Program Files\Google\Google Talk\googletalk.exe" /nomutex(Assuming you kept the default install directory).
Click "Ok", then open two instances of Google Talk, one you will have to change the login info in order to use your second gmail address, and there you go!
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