The metastable a(1)[Σ+3] state of PbO has been suggested as a suitable system in which to search for the electric dipole moment of the electron. We report here the development of experimental techniques allowing high-sensitivity measurements of Zeeman and Stark effects in this system, similar to those required for such a search. We observe Zeeman quantum beats in fluorescence from a vapor cell of PbO, with shot-noise limited extraction of the quantum beat frequencies, high counting rates, and long coherence times. We argue that improvement in sensitivity to the electron electric dipole moment by at least 2 orders of magnitude appears possible using these techniques.