What exercises most directly impact and strengthen the posterior rotators and scapular muscles of the back?
Heavysprout, I give priority to external rotation exercises over internal rotation. On my list of favorites are
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Pullovers; full ROM (Machine)
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Pull-ups, Chin-ups, Mixed-Grip Pull-ups
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Hammer Strength High & Low Rows
(Hold at top w/ full scapular retraction) -
T-Bar Rows & Bent-Over Rows
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Reverse Pec Dec; External Rotation Machine or Bent-Over Lateral Raises w/ Dumbbells
Another thing you can do on seated cable rows is fully extend the weight, retract and set scapula, pull the weight in, hold at the top for a couple of seconds.
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Check out this article for ideas.