It is very possible.
You can go about it two ways.
If you already have user files in the SSD you can move them usign the command line (to preserve permissions since the finder copy can sometimes mess it up). The command would go something like this:
sudo cp -Rvp /Volumes/[Original hard Drive - SSD]/Users/[Username - Replace for the username] /Volumes/[New Hard drive]/Users/[Username - Replace for the username]
Once he copying completes, you need a different account with administrative privileges to modify the users home folder by opening Users and Groups on the System preferences, pressing on the lock to unlock the users properties and right clicking on the user in the System settings/Accounts menu and pointing to the new location. You should restart and everything should be up and running.
If you are setting it up from scratch, you just need to create the account and right click on it (Advanced) and point to a different location in the new hard drive.
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I have uploaded some pics to try to explain the steps.
Good luck.