Over the past decades, radioanalytical methods for environmental monitoring of plutonium (Pu) isotopes from contaminated soils were developed to respond in case of a nuclear accident but also for routine analyses. In this paper we prove the possibility of on-site analysis of plutonium using alpha particle spectrometry. Tests are performed with two types of soils: a “brown” soil and a “sandy” soil, both spiked with 242Pu. The proposed method starts with leaching the soil, then separating the radionuclides of interest through a TEVA column and finally preparing counting planchets for alpha-spectrometry analyses. The aim of this work was to obtain a fast and reliable procedure, from the sample preparation to the analysis, applicable directly in the field and lasting no longer than a working day. The testing involved several parameters, such as the soil-to-liquid ratio, the acid molarity, the influence of a purification step, the source preparation. For each procedure defined, the time and the recovery rates of 242Pu were recorded and compared. Results have proven that the recovery rates increase with the solid-to-liquid ratio, with the acid molarity, with the purification step but decrease with the mixing time. The two methods used for source preparation showed similar results and the sources were measured by alpha spectrometry, using two different counting devices. The final selected sample preparation procedure has a throughput of 3 h, with recovery rates of 33.8 ± 3.1% for the “brown” soil and 77.3 ± 9.2% for the “sandy” soil and is suitable for a field application.