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Just a quick follow up to say that worked perfectly using the paste exactly trick. The OS wouldn't let me copy/paste the actual Library folder, so the trick is not to select the user Library folder, but the inner contents. On a side note, you'll probably have make the user Library visible via the terminal.
After copying across all the Library contents you'll have to change the user startup under advanced options in the system preference user settings before restarting. Always make a backup first using SuperDuper!
To make this work I've had to leave a lot of the big things like the iMovie database and music library on the old SATA, but these can easily be accessed via symlinks. Overall this is a much better solution than I had previously.
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