For this type of thing there are IMO two approaches:
1 - Using Named Graphs in a Triple Store
Rather than editing an actual fixed file you use a Graph which is stored as a named graph in a Triple Store that supports triple level updates (i.e. you can change individual Triples in a Graph). For example you could use a store like Virtuoso or a Jena based store (Jena SDB/TDB) to do this, basically any store that supports the SPARUL language or has it's own equivalent.
2 - Using a fixed RDF file and altering it
From your mention of XPath I assume that you are intending to store your file as RDF/XML. While XPath would potentially work for this it's going to be dependent on the exact serialization of your file and may get very complex. If your app is going to allow users to submit and edit their own files then they'll be no guarantees over how the RDF has been serialized into RDF/XML so your XPath expressions might not work. If you control all the serialization and processing of the RDF/XML then you can keep it in a format that your XPath will work on.
From my point of view the simplest way to do this approach is to load the file into memory using an appropriate RDF library, manipulate it in memory and then persist the whole thing back to disk when the user is done (or at regular intervals or whatever is appropriate to your application)