Fluorescence spectroscopy uses a beam of light that excites the electrons in molecules of certain compounds, and causes them to emit light. That light is directed towards a filter and onto a detector for measurement and identification of the molecule or changes in the molecule.
The excitation spectrum in normal situations ought to look like the absorbance spectrum.
When you scan the excitation wavelength, the fluorescence detected depends on photons absorbed (the absorbance spectrum) and quantum yield of fluorescence. If the fluorescence quantum yield varies with excitation then you will see deviations.
if you want to prove energy or excitation transfer as a quenching mechanism, then if you excite molecule A bit observe fluorescence from the acceptor molecule B, this is shown to have happened. Since both A and B may absorb at a given wavelength, showing that an excitation spectrum of A can be detected at the fluorescence wavelength of B is stronger evidence.
quenching without observing fluorescence from the acceptor suggests that it might be electron transfer but does not prove it. Proof requires demonstrating that A+ or B- exist through other means.