This is the guide I wrote for myself a few years ago, it should still be the same for Mavericks... YMMV.
Last updated: 9/6/2012
Source:
TUAW
Applies to: Mountain Lion (though basically the same steps at least back to Snow Leopard)
How to Move the Home Folder in OS X
(from one drive to another drive)
Click on Macintosh HD in the Finder and open the Users folder. In here you will find a folder named after your shortname. This is your home folder. As it is currently your active home folder it will have a house icon assigned to it. Copy this folder to the 2nd hardrive by simply dragging it (moving files / folders to a 2nd volume in OS X only copies the content, it doesnt remove it from its original location). Note: The copied folder will not have the house icon as it is not yet recognized as you active home folder. We will change this in the following steps.
Open the System Preferences application from either the Dock, the Applications folder or from the Apple menu.
Click on the "Users & Groups" icon in the System section.
After entering your password to unlock the padlock, CTL-Click (or right click if you have this enabled for your mouse) on the active admin account (from the list of user accounts in the left pane) to reveal an Advanced Options contextual menu. Select this item.
You will be presented with a pane full of advanced settings (and also a warning about how you should only change these settings if you know what you are doing!). Ignore all of these settings except for the Home Directory option. This is the path that OS X uses to locate your home folder when you login. It should say: /Users/shortname
Click on the Choose button, and browse to the home folder in the new location (this will be the folder you moved in Step 1 which will be named after your shortname). After you select the new location, the Home directory path should change to something like: /Volumes/shortname.
OS X will continue to use the original home folder until you restart. So restart the computer and login as normal. To confirm that the new home folder is now active, browse to the folder you copied to the 2nd hardrive and check it has the house icon assigned to it. Now that your home folder is successfully located on your 2nd drive, you can delete the original home folder in the Users folder. It should now have a generic folder icon as it is no longer the active home folder.
NOTE: I recommend having at least one account with "administrator privileges" on your boot drive. If you don't have one, create one.