Go to Profiles.
Create a new Profile, call it Twitch.
In Settings->Stream, link your Twitch account.
You can only stream to one service at a time. Profiles let you create presets for things like which service you're streaming to, what bitrate to use, and what resolution and framerate to stream at.
I'd also strongly recommend watching the Nerd or Die OBS Tutorial video series. It covers basic functionality like this.
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