Since an emission spectra represents electrons moving back down to different energy levels and releasing a photon with the energy difference, wouldn't the emission spectra of a star be temperature dependant? Wouldn't the hotter stars have more electrons in higher energy states and so have larger energy releases when they fall back? So my question is do we see that hotter stars have a more pronounced emission spectra in the high frequency range of light, if not, why?
This is not how stars emit light. Stellar emission is thermal radiation for the most part. So while it is true that stars with higher temperatures emit spectra that are shifted to the shorter wavelengths of light, it has nothing to do with excitation and recombination processes in atoms.
There are often certain lines missing in stellar spectra, which is due to the inverse effect you are describing. Atoms on the outermost layers and surrounding a star can absorb some of the thermal radiation to excite electrons in their shells. These lines can be used to determine which elements are present in the vicinity of a star.