The former England midfielder and I’m A Celebrity winner, 36, will make her debut as the blue team captain on the sports-themed quiz show when it returns for its 18th series on October 25.
The Sky original series will see former England footballer Jamie Redknapp captain the red team while comedian Romesh Ranganathan will host.
Speaking about her highlights from the show ahead of its launch, she said: “There are too many. My duet with Peter Andre – a lifetime ambition completed!”
Guests for the upcoming series include England goalkeeper Mary Earps, former Welsh footballer Gareth Bale, ex-England cricketer Stuart Broad, England midfielder James Maddison and comedians Katherine Ryan and Maisie Adam.
Scott said she enjoyed her time with all the guests but noted that her friend Earps was “brilliant and threw herself at everything”.
Reflecting on who she would like on the show in future series, she revealed she would be keen to get Hollyoaks actor Owen Warner, her former campmate on I’m A Celebrity… Get Me Out Of Here!, on the show.
Joining her on the red team is pundit and former England footballer Micah Richards while comedian and presenter Mo Gilligan has joined Redknapp’s team for this series.
Scott revealed the show had brought out a “sports rivalry” between her and Redknapp.
“He really wants to win and so do I, so that’s made it very interesting at times”, she said.
“But it’s been an absolute pleasure to come up against him.
To mark Sunderland-born Scott’s appointment as the new captain, a statue was made which stood alongside the Angel of the North as a short-term tourist installation to honour her sporting achievements.
Ranganathan praised Scott as an “amazing addition” to the show, adding: “She is a proper footballing legend and is naturally very witty.
“She has slotted into the team incredibly well. I think people are going to be blown away by how good she is when the show comes out.”
He also admitted Scott and her teammate Richards could not have “more opposing energies” but feels that is why they work well together.
“Micah has been great at welcoming Jill to the show, and they get on brilliantly”, he added.
“They bounce off each other really well – Micah like an excitable puppy and Jill like the owner of a puppy that’s too excitable.”
TV presenter and former cricketer Andrew “Freddie” Flintoff, who was injured in a car crash while filming Top Gear earlier this year, previously captained the blue team in series 16.
Among the games returning of the series will be Leap of Faith, but with a twist which Ranganathan revealed might make it the “scariest challenge” the show has done.
Season 18 of A League of Their Own will launch on October 25.
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