I would consider defining a substructure that higher levels use to store data, a little like a mini file system inside the file.
For example, even though your file format is going to store application-specific data, I would consider defining records / streams etc. inside the file in such a way that application-agnostic code is able to understand the layout of the file, but not of course understand the opaque payloads.
Let's get a little more concrete. Consider the usual ways of storing data in memory: generally they can be boiled down to either contiguous expandable arrays / lists, pointer/reference-based graphs, and binary blobs of data in particular formats.
Thus, it may be fruitful to define the binary file format along similar lines. Use record headers which indicate the length and composition of the following data, whether it's in the form of an array (a list of identically-typed records), references (offsets to other records in the file), or data blobs (e.g. string data in a particular encoding, but not containing any references).
If carefully designed, this can permit the file format to be used not just for persisting data in and out all in one go, but on an incremental, as-needed basis. If the substructure is properly designed, it can be application agnostic yet still permit e.g. a garbage collection application to be written, which understands the blobs, arrays and reference record types, and is able to trace through the file and eliminate unused records (i.e. records that are no longer pointed to).
That's just one idea. Other places to look for ideas are in general file system designs, or relational database physical storage strategies.
Of course, depending on your requirements, this may be overkill. You may simply be after a binary format for persisting in-memory data, in which case an approach to consider is tagged records.
In this approach, every piece of data is prefixed with a tag. The tag indicates the type of the immediately following data, and possibly its length and name. Lists may be suffixed with an "end-list" tag that has no payload. The tag may have an embedded identifier, so tags that aren't understood can be ignored by the serialization mechanism when it's reading things in. It's a bit like XML in this respect, except using binary idioms instead.
Actually, XML is a good place to look for long-term longevity of a file format. Look at its namespacing capabilities. If you construct your reading and writing code carefully, it ought to be possible to write applications that preserve the location and content of tagged (recursively) data they don't understand, possibly because it's been written by a later version of the same application.