Membership Provider is limited to 1 email account per account holder. You can attach custom attributes for each account using Membership Profile. So your secondary email would simply be an attribute of the user's profile.
Here is a great article explaining how to do this.
It is possible, but not with any of the built-in membership providers. You will need to implement your own. Just know that your design will come down to ensuring that e-mail is unique in the table and is linked to a single user account (many-to-one).
This will require a separate table in the database for the many e-mails a user may have.
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