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Ply refers to the number of strands a yarn is composed of. The term ply is misleading. Some people assume that the more plys a yarn has, the thicker it is. Not true. Some bulky yarns have only 2 plys and some multi-ply yarns are as thin as baby/fingering weight. It is better to look for yarn in terms of weight such as baby, sport, worsted, bulky, super-bulky. These refer to the thickness. This is also how most yarns are labeled.
The answer lies in the twist. Twisting fiber imparts strength to a yarn. It makes the fibers harder to pull apart lengthways and the yarn therefore harder to break. You can twist in either direction. If you hold a length of fiber one end and twist the far end to the left you get an S twist in your yarn. If you twist to the right instead you get a Z twist. Most manufactured single plies are spun with a Z twist. To ply these Z-spun singles together they are spun with an S twist to give a balanced plied yarn.