You are getting a few things conflated:
With folder redirection you move aside and replace folders in the user’s home directory (presumably a network home directory) with local resources. This can have a huge impact with things like the Cache directory when you are using network home directories.
The second thing is Home Folder Syncing with “Mobile” users. This allows you to sync your local home folder with the folder designated as your network home folder, presumably by an OD or AD server.
Both of these are setup through MCX/WorkgroupManager. I think what you want is a Mobile user, but it is going to take a bit of work to get that crafted right (it is a complex thing).
Oh.. and GPO’s are not used on MacOS X.
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