Some people use starch on everything. I am not one of those people. I agree with dakotamaid that if you make one little oops while ironing, you could have a bigger wrinkle than when you started.
Before they came up with spray starch, Mom would prepare starch by mixing powder with water, then heating it on the stove. Then, all cottons that needed ironing were dipped in a watered down solution and hung out to dry. After it was dry, we would dampen the pieces with water, fold it up, wrap it in a towel, and let it "rest" in the refrigerator for a few hours before pressing with a dry iron. I'm telling you this because you can try duplicating this by taking the fabric, spraying it with spray starch, and then fold, wrap and refrigerate. The starch spreads evenly into the fabric while it is resting and irons smoothly.