MySQL is an RDBMS, Relational Data Base Management System.
The term Relational is used because the data is stored such that rows in one table are related to rows in other tables.
In this case, rows in the pictures table are related to rows in the profiles table when the id column has the same value in both tables. So the JOIN is used to match the rows up and return you a single set of data from the combination, in this case a set of (picture, username) pairs.
SQL is very powerful, it's worth putting some time into learning. There are plenty of books and other sources online.