The two main rules for assigning probabilities:
Each outcome's probability (let's call it P(E)) has to be between 0 and 1. Imagine a scale from 0 (impossible) to 1 (guaranteed). The probability sits somewhere on this scale.
The sum of ALL the probabilities for every outcome in the experiment must equal 1. This makes sense because all the outcomes together represent every possibility, so their combined probability is 1 (certain to happen)