Exhaust gasses can be up in the 1200-1600 F range depending on mixture ratios and power settings. I've seen some headers glow red (950-1400f) with really lean mixtures under loaded high power.
However, a header is always shedding accepted heat from the exhaust to the lower temp surrounding air, so it's almost always cooler than the actual exhaust gas temperature.
A thick coat of paint can interfere with the heat exchange process on the outside.