Marvel's Most Wanted has been said to be a spin-off then definitively stated by the producers to be a... not-a-spin-off.
Uh. What does that mean?
You are taking two characters from one series and putting them into another. That reeks of "spin-off".
Maybe the characters aren't "spinning off" the original show. Maybe they are staying with the original show and the new show uses their characters without detracting from the characters utilization in the original show - in this case, Marvel's Agents of S.H.I.E.L.D.
You can't really do that, can you?
Well, you can. And,
I can think of a couple of ways you can do that.
First, you can create a prequel series to Agents of S.H.I.E.L.D. In this scenario, all of the history between the two characters becomes available to you. All of the innuendos and historical references in AoS are expandable (and exploitable: "Hey! I remember when they mentioned that on AoS!").
Take 5 years off each character (maybe 7 or 8 - you wouldn't want to limit the duration of your series by bumping up into Season Two of AoS while still plotting out MMW!). Create all the stories of romance, spite, romance, betrayal, romance, marriage, betrayal... you get the picture.
These guys are secret agents and/or mercenaries, after all.
But, that would be kind of cheesy.
There wouldn't be enough difference in time period for the new show to become a "period piece" ala Marvel's magnificent Agent Carter and their exploits couldn't be too explosive because they haven't been referenced, really, in any other "current" Marvel adventure.
Second, you could make Marvel's Most Wanted the mid-season break (again, ala Marvel's Agent Carter) for one of their other shows. MAC already has that slot for AoS, so, maybe MMW becomes the mid-season break for Marvel's new comedy series, Damage Control, or Marvel's other as yet unnamed new comedy venture.
Or, it could be the breakisodes for that John Ridley Project that is still in the works, apparently. This would allow the second, still unnamed, comedy to provide the breakisodes for Damage Control keeping the fare more similar in the time slots.
This way really works.
While Marvel is spending its winter retooling their primary show, Agents of S.H.I.E.L.D., Agents Hunter and Morse are sent out on missions (a mission?) that are (is?) detailed in MMW. Coulson could even make random appearances (ala Nick Fury with the different Avenger characters) as could Daisy and any of the other AoS stars.
Plus, new show runners for MMW will have some most excellent ideas. And, they could feed some of those ideas back into AoS further invigorating Marvel's television flagship show.