You will have to get all the old paint off, its not a high heat paint, just there to protect them until they are mounted. The best stuff I have used is the POR20 header paint. This is a brite alumium finish. If there is any rust you need to remove it too, I used muriatic acid from the hardware store to remove the rust on a set of \6 headers.
The picture below is are the \6 headers after 2.5 years and about 20k miles of driving.