Air can only hold so much water. At 100% humidity, that is the point it cannot hold any more. So, the higher the humidity, the less sweating/being wet can cool you down. The hotter the air, the more water it can hold
The dew point is the temperature at which water will condense out of the air. The actual equations are complex, but in day to day life, it is a measure of how hot it *feels*. The higher the dew point, the hotter it feels, and the harder it is to cool down. Anything about 65F generally feels uncomfortable
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