Emails Not Forwarding - Can I Add Emails In Configuration?

I set-up the email on the website to forward to another email but it doesn't seem to be working so I'm thinking it's best to add the emails in the configuration if possible.

In Configuration > Main > Emails, can I add multiple emails in the fields below?

Payment notifications email address
Order creation admin notifications email address

Thanks!

Should I assume that I can do that in all the Email fields, excluding "From Address"?

Thanks!