I couldn't find enough information on Postgres documentations but curious to know how does btree index look like for a postgres varchar column.
Any links / explanations might be helpful.
PS: Sorry for the vague question
One good place to start is in the code ( and its contained documentation ).
Download here: http://www.postgresql.org/ftp/source/v9.4.1/
unpack the archive and look for the README under src/backend/access/nbtree/. That should give you quite a good introduction into what they're up to.
If you're ambitious and can read C code, you can have a look at the implementation in there too. Hope this helps.