Cadmium (Cd) pollution in plastic shed soils has become increasingly severe, posing a great threat to human health and social stability. Phytoremediation of cadmium pollution is an environmentally friendly and inexpensive remediation method. In this study, maize (Zea mays L.) was selected as the phytoremediation crop by a potted method, and the bioavailability of cadmium was investigated by adding exogenous elemental sulfur. The relationships among the sulfur content, maize growth, cadmium accumulation, and soil parameters were systematically studied. The results showed that, with the supplement of sulfur, the soil pH and activities of soil enzymes (urease, catalase, and sucrase) decreased gradually, and the available heavy metals (Cd, Cr, Zn, and Cu) in soil showed an upward trend. The optimal cadmium enrichment was achieved under T2 by increasing both the biomass of the maize plant and the cadmium concentration in roots and stems. However, T3 and T4 significantly inhibited the growth of maize roots and shoots, leading to a much lower plant biomass compared with that of CK (sulfur-free treatment) and T2. In addition, the cumulative cadmium was not increased because of the low accumulation of cadmium in some parts of the plant. Correlation analyses showed that the sulfur content was negatively correlated with soil pH and maize biomass (P < 0.01), and the cadmium content of whole maize was positively correlated with the dry weight of maize (P < 0.05) and the cadmium content in roots and stems (P < 0.01). In summary, to optimize cadmium phytoremediation of the plastic shed soil, an appropriate concentration of sulfur should be selected in practical applications to ensure that the biomass of the maize is maximized, and the cadmium concentration in different parts of the maize is increased or stabilized.