‘Can we get on?’ said Crowley. ‘Goodnight, miss. Get in, angel.’ Ah. Well, that explained it. She had been perfectly safe after all.
Anathema does not know that Aziraphale is an angel. She’s heard Crowley call Aziraphale angel and has assumed it has been said in a loving way, like a pet name between the two men. She knows she’s safe with them as she’s assumed them to be a gay couple.