What is the order in which you should exercise muscles for the most effective workout?

Remember: There is no specific order. But in general, consider exercising larger muscle groups like shoulders, back, chest, and legs before smaller muscle groups like bi's, tri's and calves. If you fatigue the smaller, accessory muscle prior to larger groups, it may compromise your larger muscle group exercises. But you still need variety to your exercise routines too. So don't just do the same thing.