Re-bending is a pain if the metal has been work hardened by the original bending and really needs an Oxy torch to soften it first.
But if a header is 99% ok fit, then perhaps a saw cut at that offending angle and the inclusion of some silicon tubing to rejoin the cut ends will work well enough for you.
If you are in need of a greater angle for the entire header pipe then may I suggest cutting off the header pipe from the flange, grinding a new angle and then welding the two back together again?
Or if that sounds beyond you then perhaps either the grinding an angle on the mounting flange's face itself will give enough of a difference to get you out of trouble or the inclusion of a thick wedged metal gasket (if mangulating is to be avoided at all costs) will give enough of a difference to get you out of trouble.
Good luck.