To explore the potential of plant trace elements as indicators in the search for concealed deposits within the W–Sn polymetallic mining area of Shizhuyuan, Hunan Province, this study focused on the geochemical characterization of 21 trace elements, including Ag, As, B, Bi, Cd, Mo, Ni, Pb, and U, in the stem and leaf tissues of three predominant plants in the area. A total of 126 plant samples were collected, covering an area of about 10 km2, and analyzed using ICP-MS. The best indicator plants and sampling sites were selected using multiple indicators, including the biological absorption coefficient (XBAC), the enrichment coefficient (KNJ), and the contrast coefficient (KCD). The results showed that plant leaf tissues represent the most effective sampling components for phyto-geochemical surveys in this region. Dicranopteris dichotoma exhibited markedly pronounced geochemical anomalies of Ag (0.137 µg/g), As (86.12 µg/g), Mo (0.963 µg/g), Pb (15.4 µg/g), Sb (2.03 µg/g), and Se (0.547 µg/g) and demonstrated superior absorption capabilities for Ni, Sn, Sb, Pb, and Bi in the soil, with XBAC values of 12.0, 54.2, 23.3, 2.9, and 83.9, respectively. R-type cluster analysis and factor analysis identified four distinct mineralization element combinations: (1) Sn–As, (2) Ag–Cu–Mo, (3) Pb, and (4) Bi–Sb–Se. Consequently, D. dichotoma is a viable indicator plant for the phyto-geochemical detection of concealed Ag, Bi, Mo, Pb, Sb, Se, and Sn mineralization in mining areas. The results demonstrate that using phyto-geochemical methods for mineral prospecting is feasible and has significant application value in the Shizhuyuan mining area, which is characterized by dense vegetation and complex geological conditions.