The atmosphere is not as efficient to absorb thermal radiation from the sun, compared to the ground. Plus heat rises, so even if it did warm the upper atmosphere, it wouldn’t efficiently reach your face near the ground. It’s colder in the upper atmosphere, because it doesn’t absorb as much heat from the sun, and the air is thinner. Remember in Iron man, he flew so high his suit began to ice over. Planes are pressurized not just because the air is thinner, but because it’s colder.
The warm air comes from the sun warming the ground, and in turn warming the air. You’ll notice the daily temperatures during sunny days are the warmest not when the sun is at its brightest at noon. The warmest time of day is in the afternoon, because there is a delayed transfer of heat between the ground and the air. If you stand behind a shadow You’ll feel the difference between the heat from the air and the heat from the sun.
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