If I understand correctly, the cones in the human eye work as follows: the three types have a degree of sensitivity for each wavelength. A cone is activated in a one-dimensional "degree of activation", but by itself cannot detect the wavelength of light that activates it.
If we know that only one light frequency enters the eye, then we can easily deduce what this frequency is based on the degree of activation of the three cones.
But suppose we sample a spectrum of emission from all possible spectra. What can the eye infer from the three degrees of activation? It seems like it would not be able to distinguish between many different spectra. In particular, for any given wavelength, we can create many different "scrambled" spectra that result in the same activations.
This would mean the eye has only a quite limited capacity to distinguish between spectra of emission.