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Windows 8 introduced the bare bones of automatic syncing, with many system settings and preferences syncing between devices when you sign in with a Microsoft account.
Windows 8.1 adds significant improvements to that infrastructure, including the option to sync apps and Start screen layouts across devices. When you sign in using a Microsoft account for the first time on a new device, this screen lets you choose another PC as the template for your new installation.
One of the biggest objections to Windows 8 was the way it unceremoniously dumped new users into an unfamiliar interface without a compass or a roadmap. Windows 8.1 tries to make up for that shortcoming with some hints like the one shown here, which points out how to access the charms menu. There's also a useful set of tutorials that are available on the Start screen.
More snap options
A common complaint about those "chromeless" Windows apps is that they couldn't easily be arranged on the screen. That's a special source of frustration for anyone with a large desktop display. Windows 8.1 completely overhauls the way immersive (aka Metro) apps can be arranged. More importantly, it gives app developers a way to automatically open a new window alongside an existing one. So if you click a link in an email message (as shown on the left here) the window shrinks to occupy half the screen and a browser window opens alongside.
The new snap behavior also makes it possible to open separate instances of Internet Explorer or mail, so you can have two web pages or mail messages open side by side using the touch-friendly immersive Internet Explorer or Mail app.