Two days after former Sydney boss John Longmire opted not to throw his hat in the ring, Simpson made it clear he also won't coach next year, preferring to work in the media.
Simpson, who departed West Coast in 2024, confirmed the Demons hadn't contacted him.
"I don't want to coach next year. I think I'll give it a spell," Simpson told SEN radio.
"I was thinking through it over the weekend and I know 'Horse' (Longmire) has done the same thing and it just doesn't feel like it's the right time to be available.
"Because they haven't called me. And sometimes you wait for these things because you might think 'I'm not interested', but then you get the phone call and you go, 'oh hang on, I'm wanted', and then you sort of pivot in a different way.
"But I've had a good think about it and I'm just not in the right headspace with it.Â
"... The passion to go through all the process, because once you get approached, it's turbo and you need to really be prepared and I'm not really prepared and not in the right headspace."
Outgoing Port Adelaide coach Ken Hinkley has already indicated he won't coach next year, while Longmire and Simpson aren't interested and former Essendon coach James Hird also appears out of the running.
It means former Collingwood mentor Buckley, who lost the 2018 grand final to Simpson's Eagles, now looms as the standout experienced option to replace sacked coach Simon Goodwin.
Melbourne football boss Alan Richardson told ABC radio on Sunday that the Demons hadn't spoken to Buckley.
But that seems a matter of time.
Buckley has made it clear he still has the desire to coach at the top level.
Last week, he told SEN radio he would take the Demons' call and labelled the job "compelling", but indicated he would need to be convinced to jump back into an AFL hot seat.
The former Collingwood champion spoke again on radio on Monday and insisted he wasn't going to deliver "blow-by-blows" reaction to the Melbourne recruitment process.
"I've been out of coaching for a little bit longer, so I know exactly where they're at," Buckley told SEN.
"And I'm still working out whether I'm there or whether I'm in. So I'm well and truly on the fence."
Buckley said it wasn't uncomfortable to have some regard him as the presumptive candidate, insisting that was "irrelevant".
Of the untested options, Magpies assistant Hayden Skipworth appears top of the pile.
Brisbane coach Chris Fagan last week said Lions football boss Danny Daly had the "capacity" to become a senior coach.
Demons caretaker coach Troy Chaplin will not pursue the full-time role.
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