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For the actual steam/gaming account on SteamOS valve uses their own compositor and for desktop mode they have a second user which uses the standard gnome compositor. That way the OS actually switches users to go into Desktop mode, where you could be running Steam as well, but then it'd be easier and more convenient to use a distribution intended for actual full-on desktop use, like Ubuntu, Debian, Mint, Fedora, openSUSE etc. pp.
So the account intended to use steam on actually doesn't have a desktop running, so your second screen would probably be just black.
Short Answer: You can probably setup dual monitors fairly easily within the desktop/gnome environment of SteamOS, it does however not make a lot of sense to do that as it's not the intended environment to enjoy your games on SteamOS. And in the actual "Big Picture"-only environment you'd have nothing to display on your second screen.
If you only want your second monitor for the purpose of making desktop mode more convenient for your personal use, you're good to go.
If you want a game running in fullscreen while having other windows on the second monitor, that's technically possible too, but it makes more sense to go for a full-on desktop distribution in that case.
No matter how "steam" account is set up, for me at least, big picture default log in always uses both screens in duplicate mode.
This in turn makes settings in Big Picture disabled and all kinds of crap. It's most likely an AMD issue, but be that as it may ...
For now this beta prefers to run on one HDMI screen, as that is expected of a Steam Machine. I'm sure we will get better hardware config control in the future to handle multi display and multi audio device machines.
As a workaround I manually log in to "desktop" account via GNOME session and then run Steam from there in desktop client mode. After that even Big Picture works on single screen. Since AMD machines are not officially supported this is more than I hoped to achieve. :)
Around the 6:40 mark linus shows of triple monitor eyefinity through game stream
This is my major annoyance with SteamOS right now... having to disconnect my second monitor any time I want to boot it. I have a lot of cables, it's a hassle to disconnect my monitor every time I boot... and I don't plan on doing much more with SteamOS until this issue is addressed.