Modelling the inter-relationships between litter accumulation and plant–soil feedback is a major challenge to predict natural and agricultural ecosystem dynamics. At increasing levels of undecomposed plant litter, seedling growth tends to show a multi-faceted response trend, characterised by a peak of positive stimulation at lower dosage followed by inhibition at higher dosage. In this study, a new logistic model was developed to describe such trend and disentangle substrate-specific positive and negative effects of plant litter. The model was tested on 35 litter types applied to the common phytometer Lepidium sativum; all litter types were collected in Mediterranean shrublands of Campania region (southern Italy). Model fitting resulted to be generally higher relative to the widely used linear log response model, although in only half of the cases it also gave more parsimonious results in terms of minimising information loss. Positive and negative effects of plant litter resulted to be uncorrelated, showing that the overall trend is probably the result of the combined action of separate factors rather than the effect of a single factor behaving differently at the different doses. The results of this work provide new tools to finely tune the optimal doses in experiments on hormesis and litter phytotoxicity, through the identification of the most suited doses to centre the range of nearly linear response to litter concentration. A wide screening is also presented on the phytotoxicity profiles of a number of spontaneous plant species widely distributed in the Mediterranean area.