This study is concerned with the film cooling effectiveness of the flow issuing from the gap between the nozzle guide vane (NGV) and the transition duct on the NGV endwall, i.e., the purge slot. Different slot widths, positions, and injection angles were examined in order to represent changes due to thermal expansion as well as design modifications. Apart from these geometric variations, different blowing ratios (BRs) and density ratios (DRs) were realized to investigate the effects of the interaction between secondary flow and film cooling effectiveness. The experimental tests were performed in a linear scale-1 cascade equipped with four highly loaded turbine vanes at the Institute of Fluid Mechanics and Fluid Machinery of the University of Kaiserslautern. The mainstream flow parameters were, with a Reynolds number of 300,000 and a Mach number (outlet) of 0.6, set to meet real engine conditions. By using various flow conditioners, periodic flow was obtained in the region of interest (ROI). The adiabatic film cooling effectiveness was determined using the pressure sensitive paint (PSP) technique. In this context, nitrogen and carbon dioxide were used as tracer gases realizing two different density ratios DR = 1.0 and 1.6. The investigation was conducted for a broad range of blowing ratios with 0.25 ≤ BR ≤ 1.50. In combination with 10 geometry variations and the aforementioned blowing and density ratio variations, 100 single operating points were investigated. For a better understanding of the coolant distribution, the secondary flows on the endwall were visualized by oil dye. The measurement results will be discussed based on the areal distribution of film cooling effectiveness, its lateral spanwise, as well as its area average. The results will provide a better insight into various parametric effects of gap variations on turbine vane endwall film cooling performance—notably under realistic engine conditions.