I need to load large models and other structured binary data on an older CD-based game console as efficiently as possible. What's the best way to do it? The data will be exported from a Python application. This is a pretty elaborate hobby project.
Requierements:

no reliance on fully standard compliant STL - i might use uSTL though.
as little overhead as possible. Aim for a solution so good. that it could be used on the original Playstation, and yet as modern and elegant as possible.
no backward/forward compatibility necessary.
no copying of large chunks around - preferably files get loaded into RAM in background, and all large chunks accessed directly from there later.
should not rely on the target having the same endianness and alignment, i.e. a C plugin in Python which dumps its structs to disc would not be a very good idea.
should allow to move the loaded data around, as with individual files 1/3 the RAM size, fragmentation might be an issue. No MMU to abuse.
robustness is a great bonus, as my attention span is very short, i.e. i'd change saving part of the code and forget the loading one or vice versa, so at least a dumb safeguard would be nice.
exchangeability between loaded data and runtime-generated data without runtime overhead and without severe memory management issues would be a nice bonus.

I kind of have a semi-plan of parsing in Python trivial, limited-syntax C headers which would use structs with offsets instead of pointers, and convenience wrapper structs/classes in the main app with getters which would convert offsets to properly typed pointers/references, but i'd like to hear your suggestions.
Clarification: the request is primarily about data loading framework and memory management issues.
Consider storing your data as BLOBs in a SQLite DB. SQLite is extremely portable and lighweight, ANSI C, has both C++ and Python interfaces. This will take care of large files, no fragmentation, variable-length records with fast access, and so on. The rest is just serialization of structs to these BLOBs.
Optimal datafile format loading on a game console