What they are trying to do is obvious: leverage the ex-player's knowledge of and relationships with current player's/coaches, as well as their connections with the clubs under discussion and perceived popularity.
It's the dumbest idea though, as this is television. You need engaging personalities with charisma to shine through to the viewers, and a bit of intelligence as well. You're absolutely right about the chemistry bit. Lescott Balo Ferdinand and Cesc? I'd rather be poked in the eye with a stick.
They are trying to imitate the show "Inside the NBA" in my opinion without taking into account the factors that make the show "work". The analysts - Shaq, Charles Barkley and Kenny Smith all are very knowledgeable about basketball and genuinely enjoy being around one another, and you can't manufacture that. And the host Ernie Johnson is simply the most charming, easy going and unassuming person on television, but is actually as big a star as the others. They bring in others to fill in from time to time but those four are irreplaceable. At its best, the show is fun and informative at the same time.