Can you elaborate? Where is the 'switch to offline mode' button? Why does 'Play Offline' frequently not work? If by 'offline mode' you are referring to 'play offline', then my question still stands: what are the pre-requisites for playing offline?
when you open Steam, on the top left click on "Steam" and select "Go offline". It will restart and so on. There are no per-requisites that I know of, I do it all the time and I do nothing special. The reason why it doesn't work all the time is similar with why automatic updates don't work all the time - because sometimes Steam does whatever it wants to.
If you want to be sure to play offline, unplug your internet before opening steam so you won't sign in.