Not easier, but vastly more flexible.
Sure, it's completely trivial to read a file containing an array of C structs of metadata and offsets into a blob of concatenated PNGs: just mmap the thing, and your main data structure is sitting right there in memory.
But problems start arising when you need to update the structure of that metadata. Add some more fields. Some more structured, multi-value fields, referring to multiple entities in your increasingly complex data structure. Entities which must be guaranteed to exist. And perform modifications concurrently, from multiple processes. And have the file not get corrupted when something kills a writer process in the middle of writing...
Databases are slow and overkill for the simple case, but they certainly make adding unexpected requested features much easier. And it can be expected that you will get unexpected feature requests.