Ashton, 38, played 153 times for Salop between 2004 and 2009, after initially arriving at the club on loan from Tranmere.
He left in 2009 to join Macclesfield, before spells with Chester, Wrexham, Barrow and Southport.
He ended his playing days in the Cymru Premier with Llandudno and Cefn Druids, and took over as manager of the latter in 2022.
After one season in charge of the Cymru North side he stepped away, and has now taken over at near neighbours Albion on a two year deal.
The ex-Salop left back said: "I am really excited to have been offered the opportunity to join Cefn Albion Football Club.
"Following my conversation with the chairman and learning about his ambitious vision for the club, taking on this role was an easy decision for me.
"I’m looking forward to meeting what is already a strong group of players and a dedicated set of volunteers, as we embark on an exciting journey together.”