I've written an experimental tool for presenting PostgreSQL relation files in a hex editor with annotations/tags and tooltips that show the structure of the data and its content, including bit field values. This tool is called pg_hexedit, and is available from:
pg_hexedit is built on top of the open source, cross-platform GUI hex editor wxHexEditor. Since it's an experimental tool that is primarily made available for educational purposes, you are well advised to not use it on any data directory that isn't entirely disposable. It may cause data corruption. Opening a Postgres relation file in a hex editor while the server is running is a fundamentally unsafe thing to do if you care about your data. Use of the tool should be limited to throwaway installations on users' personal machines.