A method for classifying a sample based upon a complete spectral analysis. The sample is illuminated with penetrating radiation and an initial complete spectral analysis is performed based on spectral resolution of resonant fluorescence lines emitted at the surface, or within the volume, of the sample. If the initial complete spectral analysis yields the composition of the sample to within acceptable limits, analysis values are output to the user. Otherwise, further analysis, informed by the results if the initial complete spectral analysis, is performed.