Portable X-ray fluorescence (pXRF) sensors allow one to collect digital data in a practical and environmentally friendly way, as a complementary method to traditional laboratory analyses. This work aimed to assess the performance of a pXRF sensor to predict exchangeable nutrients in soil samples by using two contrasting strategies of sample preparation: pressed pellets and loose powder (<2 mm). Pellets were prepared using soil and a cellulose binder at 10% w w−1 followed by grinding for 20 min. Sample homogeneity was probed by X-ray fluorescence microanalysis. Exchangeable nutrients were assessed by pXRF furnished with a Rh X-ray tube and silicon drift detector. The calibration models were obtained using 58 soil samples and leave-one-out cross-validation. The predictive capabilities of the models were appropriate for both exchangeable K (ex-K) and Ca (ex-Ca) determinations with R2 ≥ 0.76 and RPIQ > 2.5. Although XRF analysis of pressed pellets allowed a slight gain in performance over loose powder samples for the prediction of ex-K and ex-Ca, satisfactory performances were also obtained with loose powders, which require minimal sample preparation. The prediction models with local samples showed promising results and encourage more detailed investigations for the application of pXRF in tropical soils.