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I tried the steam://flushconfig trick, did not help.
Edit: Actually, it seems it's just the launch when computer starts that won't stick.
The exact instructions- https://support.steampowered.com/kb_article.php?ref=3134-TIAL-4638
This is probably not very helpful to you, but that sounds just like this user's issue..
http://steamcommunity.com/discussions/forum/1/357288572129312927/
We tried several suggestions in that thread also, but I don't think OP ever found a solution. Not sure...
-Cut/Paste steamapps folder to desktop
-Uninstall Steam
-Reboot
-Install Steam
-Cup/Paste steamapps folder in Steam folder
Right now the setting is on, i did not verify if i can modify it because download is almost capped for the month.
- Steam.exe (application)
- DepotCache (folder)
- Skins (folder) If you use any custom skins
- SteamApps (folder)
- UserData (folder)
- #SSFN (file)
Best bet also is never install Steam to Program Files / Program Files (x86)
Otherwise u do not actually have full control of the files/folders here; among other reasons, such as Windows UAC.
Then right click Steam.exe > click Run As Admin
Steam Client will be redownloaded into that folder.
Just tried this since I noticed the problem after a hardware upgrade and fresh windows install, but no luck.
No fixes yet. :(