Apple - How to prevent app from auto starting

There are two places for LaunchAgents to be called from:

/Library/LaunchAgents - this launches a process at login for every user
~/Library/LaunchAgents - this launches a process at login for a specific user.

The Spotify startup plist is found in the latter; the com.spotify.webhelper.plist allows you to open Spotify via the web.

Issue the command launchctl list | grep -i spotify and you should find (up to) two plists that are loaded:

$ launchctl list | grep spotify
-       0   com.spotify.client.startuphelper
9087    0   com.spotify.webhelper

To unload them, you can uncheck the option in Advanced Settings (Command,)

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Or...

You can issue the command:

$ launchctl unload com.spotify.client.startuphelper.plist

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