Not to do the MOVE, but to set the path. Unlock it first I think (changed from Snow Leopard btw where it was handled by "Accounts")
You do just copy, in Finder by hand; or, you can use CCC and uncheck all but user sub folders.
You also want to move or clone the system sans user home folder, but... strong 'but' ,.... I would leave a basic default /Users/user-account-folder/Library so you always will have a small 4GB account on the boot drive. In fact when using an SSD it is best performance to leave that there on boot drive and just move all the data documents media and other files and folders.
iTunes, iPhoto - every program is happy to use any location without relocating user.
From what you have, to two new drives, system and a data/media drive, cloned with CCC
Leave your current drive as backup until you are ready to erase and make it either a backup system or a backup of data.
How to relocate system and user data to another drive:
http://support.apple.com/kb/HT4337
http://chris.pirillo.com/how-to-move-the-home-folder-in-os-x-and-why/