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We characterize the coherent dynamics of a two-level quantum emitter driven by a pair of symmetrically-detuned phase-locked pulses. The promise of dichromatic excitation is to spectrally isolate the excitation laser from the quantum emission, enabling background-free photon extraction from the emitter. Paradoxically, we find that excitation is not possible without spectral overlap between the exciting pulse and the quantum emitter transition for ideal two-level systems due to cancellation of the accumulated pulse area. However, any additional interactions that interfere with cancellation of the accumulated pulse area may lead to a finite stationary population inversion. Our spectroscopic results of a solid-state two-level system show that while coupling to lattice vibrations helps to improve the inversion efficiency up to 50\% under symmetric driving, coherent population control and a larger amount of inversion are possible using asymmetric dichromatic excitation, which we achieve by adjusting the ratio of the intensities between the red and blue-detuned pulses. Our measured results, supported by simulations using a real-time path-integral method, offer a new perspective towards realising efficient, background-free photon generation and extraction.