Multiple mail accounts work just fine.
Apple mail mailboxes cannot be password protected.
Mail messages can conceivably be forwarded to a different email account, but that’s not without its own issues.
Mail accounts can be marked as offline within mail, but that’s not a password-protected operation.
I don’t know of a way to cause mail to prompt for the mail server password for each connection.
If an untrusted second party has access to your Mac and to your Mac login password, you’re already headed for deep trouble and well before any discussions of mail.
Probably the closest option with only the default tools is a second Mac login with a second and parallel mail configuration.
So… what issue are you trying to address here, in general terms? In terms of security, SMTP mail leaks metadata all over the place, so isn’t the best choice for really sensitive data.