I THINK I GOT IT!
Right, so when there are many molecules in the medium between the source and the receptor (i.e. when the amount of atmosphere is greater because of the angle of emission), Mie scattering takes the lead, which is not wavelength dependent. This, in turn, means that the light observed is composed of the wavelengths that are most abundant in sunlight - oranges, yellows, reds etc. - while the rest are less observable because they are not as abundant in sunlight - blues, purples etc.
When there are fewer molecules in the medium, Rayleigh scattering takes the lead. This, however, is wavelength dependent, and it scatters the shorter wavelengths (i.e. blues) more than it scatters longer wavelengths (i.e. reds).