Cessna used a fiberglass mat on the firewall that had a black vinyl facing the cabin. The fiberglass won't smoke and it insulates the vinyl from the heat if there's an engine compartment fire.
I sure wouldn't paint anything on the firewall or use anything plastic against it.
Before the FAA put a bunch of FAR 23 into ACs, FAR 23.853 had this in it:
(f) Airplane materials located on the cabin side of the firewall must be self-extinguishing or be located at such a distance from the firewall, or otherwise protected, so that ignition will not occur if the firewall is subjected to a flame temperature of not less than 2,000 degrees F for 15 minutes. For self-extinguishing materials (except electrical wire and cable insulation and small parts that the Administrator finds would not contribute significantly to the propagation of a fire), a vertical self-extinguishing test must be conducted in accordance with Appendix F of this Part or an equivalent method approved by the Administrator. The average burn length of the material may not exceed 6 inches and the average flame time after removal of the flame source may not exceed 15 seconds. Drippings from the material test specimen may not continue to flame for more than an average of 3 seconds after falling.