Microwaves emit heat radiation to cook foods. When enough heat or energy is added to a solid it can turn liquid and then to a gas. The skin of a grape has little difficulty doing this as grapes are largely comprised of water already. As the material of the skin turns to liquid and finally to a gas, the gas from the skin turns into plasma as it is ionized. This plasma is formed via combustion of sugars and is the same material found in stars. Plasma also controls electrical fields such as the electricity in your microwave. When the fire is out, it is no longer plasma but has returned to a gaseous state. Here is a video which very briefly explains and demonstrates the phenomenon:
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