Unfortunately the peril one often encounters in such ecosystems is that "the right technical path" for working with BigCo's system is totally un-translateable to general working knowledge. By that I mean it often means having to work around specific constraints that have evolved and are specific to that BigCo and not to other BigCo's, let alone to smaller startups. It also pushes you to generally work with technology which may be a bit older, which can often mean having to accept that current best practices simply aren't at play.
I do agree with the second part of your thesis, which is that the social challenges of working in a big company are significant and can make one very well suited generally for management and leadership in a way that's not the case at a smaller company.