Although I have not worked on sprayed thick films of BaTiO3 but I have worked with PVDF (polymer films). Those can be tried using the standard way what we use for ceramics (assuming you are aware of this technique). Corona poling is also used for PVDF films. I hope the same should work for the film of BaTiO3.
it is very straight forward Amir. You just need to do the poling in the silicone oil instead of air due to its higher dielectric strength and ultimately ability to take the higher electric field.