Sedentary behaviour (SB) and physical activity (PA) have been shown to be independent modulators of healthy ageing. We thus investigated the impact of activity monitor placement on the accuracy of detecting SB and PA in older adults, as well as a novel random forest algorithm trained on data from older persons. Four monitor types (ActiGraph wGT3X-BT, ActivPAL3c VT, GENEActiv Original, and DynaPort MM+) were simultaneously worn on five anatomical sites during ten different activities by a sample of twenty older adults (70.0 (12.0) years; 10 women). The results indicated that collecting metabolic equivalent (MET) data for 60 s provided the most representative results, minimising variability. In addition, thigh-worn monitors, including ActivPAL, Random Forest, and Sedentary Sphere—Thigh, exhibited superior performance in classifying SB, with balanced accuracies ≥ 94.2%. Other monitors, such as ActiGraph, DynaPort MM+, and GENEActiv Sedentary Sphere—Wrist, demonstrated lower performance. ActivPAL and GENEActiv Random Forest outperformed other monitors in participant-specific balanced accuracies for SB classification. Only thigh-worn monitors achieved acceptable overall balanced accuracies (≥80.0%) for SB, standing, and medium-to-vigorous PA classifications. In conclusion, it is advisable to position accelerometers on the thigh, collect MET data for ≥60 s, and ideally utilise population-specific trained algorithms.