We present XMM-Newton observations of N132D, the X-ray brightest supernova remnant in the Large Magellanic Cloud, using the Reflection Grating Spectrometer (RGS), which enables high-resolution spectroscopy in the soft X-ray band. A dozen emission lines from L-shell transitions of Si, S, Ar, Ca, and Fe at intermediate charge states are newly detected in the RGS data integrating the ∼200 ks on-axis observations. This enables accurate abundance measurements of these elements, whose K-shell emission is out of the RGS bandpass. The 0.3-2.0-keV spectra require at least three components of thermal plasmas with different electron temperatures and indicate clear evidence of non-equilibrium ionization (NEI). Our detailed spectral diagnostics further reveal that the forbidden-to-resonance line ratios of O VII and Ne IX are both higher than expected for typical NEI plasmas. This enhancement could be attributed to either resonance scattering or emission induced by charge exchange in addition to a possible contribution from the superposition of multiple-temperature components, although the lack of spatial information prevents us from concluding which is most likely.