Yep when you select all subfolders every folder underneath will be backup up to the *.pst file that gets created.
Now with email accounts I am now sure I will check it out. I have never done it this way so I do not know. Maybe some else already has the answer, but when I get one I will post...
Just go into file -> Import and Export. Choose Export to a file then choose Personal Folder (.pst) the select folder(s) then choose where you want the file saved to then click finish.
Hope that helps.
Cheers
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