Effectively utilizing deep red to near-infrared (DR-NIR) phosphors to achieve the optimal performance of NIR phosphor-converted white LEDs (DR-NIR pc-wLEDs) is currently a research hotspot. In this study, an optical model of DR-NIR pc-wLEDs with virtual multilayer fluorescent films was established based on the Monte Carlo ray-tracing method. Different gradient distributions of the particles were assigned within the fluorescent film to explore their impact on the optical performance of pc-LEDs. The results show that, for the case with single-type particles, distributing more DR-NIR particles far from the blue LED chip increased the overall radiant power. The distribution of more DR-NIR particles near the chip increased the conversion ratio from blue to DR-NIR light. The ratio of the 707 nm fluorescence emission intensity to the 450 nm excitation light intensity increased from 1:0.51 to 1:0.28. For multiple-type particles, changes in the gradient distribution resulted in dual-nature changes, leading to a deterioration in the color rendering index and an increase in the correlated color temperature, while also improving the DR-NIR band ratio. The reabsorption caused by the partial overlap between the excitation band of the DR-NIR particles and the emission band of the other particles enhanced the radiant power at 707 nm. Distributing DR-NIR phosphor particles closer to the chip effectively amplified this effect. The proposed model and its results provide a solution for the forward design of particle distributions in fluorescent films to improve the luminous performance of DR-NIR pc-wLEDs.