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In System Preferences->Accounts you can view advanced options by right clicking on a user (make sure you're logged in as an admin). One of the advanced options is the location of the user's Home folder. Be careful in this dialogue - bad things can happen if you change something you're not supposed to.

I'd say that if you are going to have a 2nd HDD in your system, don't move your home folder because a lot of files in the Library folder are frequently accessed by the OS. Keep a separate iTunes, Documents, Downloads, and Pictures folder on your 2nd HDD, then make a symlink from their original location on your SSD onto the HDD. That way everything works pretty well and you get the best of both worlds, extremely fast random access on everything but large-sized files (media)
 
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