Suppose you have the alphabet $\Sigma = \{0, 1, 2, 5\}$ where the symbols represent the value of coins, and you're given the regular expression $e = (1.1) + 2$ which is supposed to describe all the possible ways you can pay for something costing $2$.
Given this, how can I deduce what . and + do? Are there agreed upon definitions for these symbols which are taken as standard?
You can't deduce it, these (standard) terms have a definition. These expressions describe sets of words.
eg let's study the expression $e$ :
The set $1\cdot 1$ contains only one element : the word $11$.
Hence, $e = \{11\} + \{2\} = \{11;2\}$.