Add External Email Address

Add External Email Address

As suggested on Password Reset page,
It is essential that Admin Users have 'other  external email  addresses' linked with their accounts in such cases of emergency. They can request the password...

My question is how do I add/link my domain email with external email address. I have looked and searched everywhere. Still not found a solution.
Note that I recently removed the original super admin and assigned to a new user.

Please help.