Finely structured ceramic coatings can be obtained by solution precursor plasma spraying. The final structure of the coating highly depends on the droplet size and velocity distribution at the injection, the evolution of the spray in the jet, and droplet breakup and collision within the spray. This paper describes a 3D model to simulate the transport phenomena and the trajectory and heating of the solution spray in the process. O’Rourke’s droplet collision model is used to take into account of the influence of droplet collision. The influence of droplet breakup is also considered by implementing TAB and Wave droplet breakup models into the plasma jet model. The effects of droplet collisions and breakup on the droplet size, velocity, and temperature distribution of the solution spray are investigated. The results indicate that droplet breakup and collision play an important role in determining the final particle size and velocity distributions on the substrate.