Perhaps thinking too deeply about this, but sitting here imagining the earth as an orange, as one is wont to do, of course.
If the peel is our atmosphere and a needle is sunlight, then it all seems clear. At high noon the needle/sunlight is piercing the peel straight down. You get the scattering that makes the sky blue, giving what is illuminated below a slight blueish/cool cast.
As the day wears on the angle of the needle gets more and more steep, until it is piercing an awful lot of peel to reach us. Here the scattering is really a lot, making the sky above blue-er, but as the sun sets the parts toward and opposite the sun start to move around the color wheel. Yellow, then losing the yellow toward orange, then on to reddish, then violet, then maybe blue/black.
So what does it mean? As artists we can do what we want. Neutralize the whites, grays, and blacks, or emphasize the color cast of the evening or morning sky.
It's all good if we consciously decide it rather than it just happening to us.