There are several muscles used to actually rotate your arm about the shoulder joint. Here is a list of some of them: pectoralis major, subscapularis, coracobrachialis, biceps brachii, supraspinatus, deltoid, latissimus dorsi, teres major and minor, infraspinatus, long head of triceps.
This is not a complete list of the muscles involved, but what it should say is that this is not a straight forward and simple mechanical motion. The only good (time efficient) exercise is to mimic the arm Wrestling motion--with a cable machine perhaps.
The role of the wrist is also a contributing factor in arm wrestling, but that is much more simple. In this part, the forearm flexors is the muscle that's used.
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