To change the settings (about:config) with the old API you would simply do:
require('sdk/preferences/service').set('media.webrtc.debug.multi_log', true);
I can't find anything on the subject for the new WebExtensions add-ons of Firefox. Is it not available yet?
Type about:config in the address bar and press Enter. A warning page may appear. Click Accept the Risk and Continue to go to the about:config page. Click Show All to view all preferences currently set in the profile or use the Search preference name box to filter the list.
To access the Preferences window, navigate to Tools → Options on Windows, Edit → Preferences on Linux, or Firefox → Preferences on OS X.
Most add-on data is stored in a folder in the Firefox user profile. However, some information is stored in the profile folder also. It's possible that there is a problem with the file(s) that store the extensions registry. Type about:support in the address bar and press enter.
This is not possible, and likely, never will be.
Source: official WebExtensions FAQ https://wiki.mozilla.org/WebExtensions/FAQ#Will_I_have_access_to_about:config_or_the_preferences.3F
Also, you might be interested in this discussion on mozilla-community.org: https://discourse.mozilla-community.org/t/webextension-read-write-access-to-about-config/12268
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