How can associate particular contacts with appropriate 'from' addresses in Mac Mail? For the most part, there is a one-to-one relationship between any given contact and the email address I select as a 'from' address.

Is there a way to configure Mac Mail to change the value of the 'from' field according to whom I am sending mail?

OS X 10.10
You can't do it by addressee.
By default it will reply from the email address you were sent the email to.
Otherwise, you could try
Prefs > Composing > Send new messages from...  Account of selected mailbox,
for an on-the-fly solution.