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A PST file is a personal storage table and a file format, Microsoft programs use, to store items like calendar events, contacts, and email messages.
In the control panel → Mail (Outlook Mail) → show profiles, your Outlook's profiles are displayed.
You can switch between different profiles, in Outlook → File → Account Settings → Change Profile.
It is very important to remember, that for your changes to take effect, you'll have to restart your Outlook.
Log into the Outlook profile, you'd like to export.
At the top left corner, press on "File" → "Open & Export" → "Import/Export" → "Export to a file" → "Outlook file (.pst).
You can temporarily import pst files into a profile, for working purposes, such as viewing or editing.
All folders will loaded in their last saved state.