two things will dictate what account shows up from the "get go."
(1) If you are replying to a message, the "from" account will default to the account that message was sent to. (so if was sent to
xyz@mac2.com, the reply will be from
xyz@mac2.com by default). Same goes for forwarding.
(2) If you are creating a new message, it will default to whichever account is listed first in the "accounts" section of your preferences. You can click and drag to put the accounts in whatever order you prefer.