Recent theories proposed a deep revision of the well-known expression for the Purcell factor, with counterintuitive effects, such as complex modal volumes and non-Lorentzian local density of states. We experimentally demonstrate these predictions in tailored coupled cavities on photonic crystal slabs with relatively low optical losses. Near-field hyperspectral imaging of quantum dot photoluminescence is proved to be a direct tool for measuring the line shape of the local density of states. The experimental results clearly evidence non-Lorentzian character, in perfect agreement with numerical and theoretical predictions. Spatial maps with deep subwavelength resolution of the real and imaginary parts of the complex mode volumes are presented. The generality of these results is confirmed by an additional set of far-field and time-resolved experiments in cavities with larger modal volume and higher quality factors.