To alter the definition of the user class, go to Setup / Classes.
CVs I would definitely create as part of the content tree. Keep the Users tree dedicated to user accounts only.
To allow users to create only one cv you could set up a workflow. Currently (afaik) the workflow eventy 'can create only one object of class X' does not exist, but it is an often requested feature - it might be a good thing if somebody coded it and we could add to the ezworkflow_collection extension.
In the meantime, you could set up an approval workflow where all cv creation is submitted to approval of admin. So admin can see it it is the 1st cv of a person or not.
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