The new era of high-resolution X-ray spectroscopy will significantly improve our understanding of the intracluster medium (ICM) by providing precise constraints on its underlying physical properties. However, spectral fitting requires reasonable assumptions on the thermal and chemical distributions of the gas. We use the output of TNG-Cluster, the newest addition to the IllustrisTNG suite of cosmological magnetohydrodynamical simulations, to provide theoretical expectations for the multiphase nature of the ICM across hundreds of $z=0$ clusters (M$_{rm {500c}} = 10^{14.0-15.3} rm {M}_odot$) based upon a realistic model for galaxy formation and evolution. We create and analyse, in an observer-like manner, end-to-end XRISM/Resolve mock observations towards cluster centres. We then systematically compare the intrinsic temperature and Fe abundance of the simulated gas with the inferred ones from spectral fitting via a variety of commonly used spectral-emission models. Our analysis suggests that models with a distribution of temperatures better describe the broad thermal distributions of the ICM, as predicted by TNG-Cluster, but still incur biases in the inferred temperature of $0.5!-!2$ keV (16th─84th percentiles). However, all spectral-emission models systematically underestimate the Fe abundance of the central ICM by 0.12 solar ($sim$ 22 per cent), almost an order of magnitude higher than the abundance errors reported in the literature, primarily due to projection effects. Selecting only strong cool-core clusters leads to minor improvements on inference quality, removing the majority of outliers but maintaining similar overall biases and cluster-to-cluster scatter.

