Multi-field inflation models and non-Bunch-Davies vacuum initial conditions both predict sizeable non-Gaussian primordial perturbations and anisotropic μ-type spectral distortions of the cosmic microwave background (CMB) blackbody. While CMB anisotropies allow us to probe non-Gaussianity at wavenumbers k ≃ 0.05 Mpc−1, μ-distortion anisotropies are related to non-Gaussianity of primordial perturbation modes with much larger wavenumbers, k ≃ 740 Mpc−1. Through cross-correlations between CMB and μ-distortion anisotropies, one can therefore shed light on the aforementioned inflation models. We investigate the ability of a future CMB satellite imager like LiteBIRD to measure μT and μE cross-power spectra between anisotropic μ-distortions and CMB temperature and E-mode polarization anisotropies in the presence of foregrounds, and derive LiteBIRD forecasts on ${f_{\rm NL}^\mu (k\simeq 740\, {\rm Mpc^{-1}})}$. We show that μE cross-correlations with CMB polarization provide more constraining power on $f_{\rm NL}^\mu$ than μT cross-correlations in the presence of foregrounds, and the joint combination of μT and μE observables adds further leverage to the detection of small-scale primordial non-Gaussianity. For multi-field inflation, we find that LiteBIRD would detect ${f_{\rm NL}^\mu }=4500$ at 5σ significance after foreground removal, and achieve a minimum error of ${\sigma (f_{\rm NL}^\mu =0) \simeq 800}$ at 68% CL by combining CMB temperature and polarization. Due to the huge dynamic range of wavenumbers between CMB and μ-distortion anisotropies, such large $f^\mu _{\rm NL}$ values would still be consistent with current CMB constraints in the case of very mild scale-dependence of primordial non-Gaussianity. Anisotropic spectral distortions thus provide a new path, complementary to CMB B-modes, to probe inflation with LiteBIRD.