Miss Simpson said Rooney drove because he was less intoxicated, but he was reportedly three times the drink-drive limit when police stopped the car.
Rooney, 31, was charged with drink driving and will appear in Magistrates Court later this month.
Coleen, who is four months pregnant, had cut short a holiday in Majorca with sons Kai, seven, Klay, four, and Kit, one and a half, returning by private jet on Friday.
Last night, Coleen and the couple's three sons remained at the home of her parents Colette and Tony McLoughlin in Liverpool, leaving Rooney at their £6million mansion in Prestbury, Cheshire - where he reportedly spent the weekend in the spare room.
She went there after confronting Everton striker Rooney at the marital home on Saturday.
A source told The Sun: "Things could change in the coming days but as things stand [Coleen's] had enough and it's finished. This was the final straw and she feels humiliated. She's planning to walk away."
A friend of Wayne added: "Wayne doesn't know what to do with himself. He's had to apologise to Coleen for lots of things in the past - but this is looking like the toughest one yet. She is absolutely raging."
According to The Sun, Coleen yesterday uploaded two poignant photos of her sons to her Instagram account with the caption: "No matter where I am they always follow me, and I hope that lasts forever."
However, the post was nowhere to be seen on her social media profile last night.
Coleen earlier phoned the party girl who is at the centre of her husband's drink-drive arrest shame and demanded that she told her "the truth".
She struck up the tense five-minute chat with mother-of-one Ms Simpson after shouting at the former England captain, 31, and said the "world is laughing at me because of you".
Coleen is said to have been in tears and screamed at her husband: "How could you do this to me while I'm pregnant? How could you be so stupid?" reports the Sunday Mirror.
Coleen also hit out the 29-year-old who was with her husband when he was pulled over by police while behind the wheel of her Volkswagen Beetle in Cheshire - and questioned why he didn't just get an Uber home before he was arrested.
After their tense phone call, Ms Simpson told The Sun on Sunday: "She asked me to tell her what happened. She seemed unhappy with the fact that we had left a nightclub in a cab together to go to my car."
After calling Ms Simpson, Coleen told her she had "nothing to be sorry for", but her friends say she is "angrier than ever".
She thought something may have happened between her husband and Ms Simpson had police not pulled him over.
Rooney is worth more than £80million and should the couple split, it could spark a tense divorce battle worth millions.
But despite her fury, some pals believe Coleen will give the marriage one last go with one friend saying: "Only time will tell whether they can rebuild their marriage. Coleen thinks she's the one who has kept the marriage together."
The confrontation came after Rooney was warned by his club that he would be transferred should he step out of line again.
Ms Simpson claimed pregnant Coleen first contacted her through Instagram while she was still on holiday in Spain.
Ms Simpson - who earns £40,000-a-year as regional sales manager for a property developer - admitted she and the footballer wanted to be away from prying eyes and that they would "perhaps" spend the night together, but she insisted to Coleen that nothing happened.
"She seemed unhappy with the fact that we had left a nightclub in a cab together to go to my car and that we shouldn't have done that," she added.
