Here we test the hypothesis that (1) plasma polymerisation is surface-dependent and (2) the substrate can promote ordered growth by studying the early stages of TEMPO plasma polymerisation. TEMPO thin films are prepared by plasma polymerisation on substrates with significantly differing chemistries and atomic roughness. We demonstrate, through high-resolution atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS), that TEMPO films are highly surface-dependent up to 30 nm, exhibiting distinct morphology and chemistry. Beyond 30 nm, the films converge to a flat, uniform structure, and are therefore considered surface-agnostic. Through a post-annealing process, we show that it is possible to grow stable single layer TEMPO coatings with an ordered arrangement on HOPG substrates. Density functional theory (DFT) provides important insights into the molecule-molecule and surface-molecule interactions, revealing an antiparallel arrangement caused by significant dipole-dipole interactions between TEMPO molecules. Moreover, the molecules are found to arrange with the NO either pointing directly upwards or downwards, perpendicular to the surface, suggesting preferential ordering of up to half of the NO groups in the molecular layer may be possible. The ability to direct and optimise the orientation of the active NO group could have significant implications for the use of TEMPO as a surface coating.