Improving the sustainability of cosmetic products while maintaining a good performance requires a deeper understanding on the way that new eco-respectful ingredients interact with hair or skin. In the case of shampoos, the surface science is dominated by the diverse changes on the hair fiber due to both chemical and physical damages that particularly affect physicochemical properties such as hydrophobicity. A native, undamaged fiber is covered with a monolayer of lipids, mainly 18-methyleicosanoic acid (18-MEA), while a highly damaged hair surface, having completely lost the protective lipids, is hydrophilic and negatively charged. Intermediate states exist, where there is a partial loss of 18-MEA (“partially damaged hair”). Here, four model surfaces have been produced, to mimic different types of hair surfaces. Their interaction with selected surfactants and polyelectrolytes (natural and synthetic) has been studied by neutron reflectometry (NR). NR can reveal hierarchical adsorption from mixtures thanks to the scattering contrast between deuterated and hydrogenous molecules. Atomic force microscopy (AFM) measurements complement the study by adding information about the in-plane structure of adsorbed species. The presence of the methyl branch of 18-MEA is found to affect the interaction of the surface with adsorbates. For surfactant/polyelectrolyte mixtures, for example, the adsorption of polymer is enhanced. Of particular interest are the results on the partially damaged hair model, as it manifests patches of hydrophobic and hydrophilic moieties; it is possible to separately observe the different adsorption behaviors to the different sites in a single experiment.