Disclaimer: I'm mostly active at chem.SE.
Chem.SE is categorized as a sciencescience site. We do often get questions that need to or should be migrated to physics.SE and biology.SE, and very rarely EarthScience.SE. In the approximately one-year time I've been active there, we never encountered a question that was ultimately migrated to any other science-categorized site.
Furthermore, IMHO the technologytechnology topic is so crowded and diverse, it's reasonable to imagine a couple of sites with no overlapping scopes, like for instance, TeX.SX and Ask Different. The same argument holds for Life/ArtsLife/Arts; like Academia and Seasoned Advice; and Culture/recreationCulture/recreation; like RPG.SE and Bicycles.SE.
That being said
I'm not suggesting anything against the current (messy?) grouping (Technology sites are about technology, even though dispersed at a broad range of topics); but how about a bit of tidying up; making some kind of sub-groups? However, for obvious reasons, one site should be able to be in more than just one of these groups.
For example; in the science tab:
- Chem.SE, physics.SE, and Biology.SE
- Math.SE, Stats.SE, physics.SE and MathOverflow1
- Theoretical Computer science and Stats.SE
as the three groups available. Now, as betas graduate (or whatever that process is now called after that meta post) they'll be added to these groups; either through a meta post and the community's decision, or through the new elected mods.
Migration paths could be set by default between the members of these sub-groups. If migration is misused in a specific path more than an arbitrary amount of times (like when the migrated post gets closed as OT on the target site), then the path'll be removed.
The final question: How should these groups be defined?
I find posting a meta discussion on per site metas and tracking people's ideas is a good way to do so. If that's too much work, you might consider speaking with the sites' mods (after all, they are expected to know their own site's scope better than other members) and reaching a conclusion on that.
1: I'm not aware whether any of these processes are applicable to MO.