You don't really need to do anything special. Any file whose path starts with /home/ will be saved to the large partition. This includes Home, Desktop, Donwnloads, Pictures, Music, Videos which show up under "Places" in the file browser. Any files outside of the home directory will be saved to the small partition. You need root permissions to create files outside of you Home directory anyway, so you don't need to worry about making mistakes here.

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