Open the stylesheet you want in the inspector by holding Ctrl and clicking on a style property from that stylesheet (on Windows, click here for Mac). Then you can add whatever you want and it updates in realtime.
For example:
p::before {
content:'TEST';
}
This will add the word 'TEST' as a prefix to any <p> tags it finds. Check it out on MDN
You can even save the stylesheet so you don't have to do it twice. Right-click inside the stylesheet and hit 'Save as'.
Inspect the element you want to add the ::before or ::after to by right clicking it and going to "Inspect Element".
Now in the Developer Tools Console, click on the plus sign icon aka. "New Style Rule". See the image below, the plus sign is next to the "Toggle Element State" button.
Next, you will be able to edit the selector so add ::before / ::after to it: