I have a Blood Angels Successor chapter that i built with the doctrine system, I'm also a Khorne Fantasy fan so I've done a fair bit of red in my time!
Never highlight red with white. It looks awful! Blood red with Salmon pink edging.... urgh.
For me this has always been the best method to get a nice even coat and is reletively fast... fastish.
Undercoat Chaos Black spray
Base coat Scortched Brown
1st layer thinned red gore
2nd layer thinned red gore
3rd layer blood red red gore 50/50
Highlights blood red.
Leave the crack in the armour and any shading Scortched brown. This will give you a more crimson darker red colour that looks more natural than a brilliant bright blood red, orange highlight.
By the way to answer your question orange highlights on red look awful and are not realistic at all. I would avoid them like the plague. I prefer earthy natural and realistic colours to comic book bolds