You work on a file locally, save it locally and from there it syncs to your cloud-based OneDrive account. That cloud-based account then syncs the files to any other devices on which you have OneDrive installed. So when you save a file to your local OneDrive folder, it ends up syncing to them all.
You can also open files directly from OneDrive, even on computers that don't have OneDrive installed, by going to OneDrive on the Web. When you make changes to documents this way, it also syncs to any devices on which OneDrive is installed.
Using OneDrive with Word 2013 is straightforward. The local \OneDrive folder is like any other folder on your PC, except that it syncs to the cloud, of course. So you can create folders, subfolders and so on underneath it, and those will get saved locally and to OneDrive in the cloud as well. Open files as you would any other, by heading to the folder. You can also click the File tab, click Open, highlight "<Your Name> OneDrive," then click the Browse button and browse to your file from there.
That's not to say that you won't get confused by OneDrive, because you well might. One issue is that, depending on your version of Windows, you might have an existing folder structure that often defaults to something like C:\Users\<Your Name>\Libraries\Documents\My Documents or C:\Users\<Your Name>\Documents\ or something similar. That means you may end up storing some files in your OneDrive folders and others in your normal Documents or My Documents folders, which can be immensely confusing. Only the files in the OneDrive folders will sync.
What to do? You can simply copy over all your existing files and folders to the OneDrive folder, and at that point, you'll have only one folder structure and everything will sync.
There's another solution as well. Open File Explorer (called Windows Explorer in versions of Windows prior to Windows 8). Right-click the OneDrive folder and select "Include in library" and then choose the library in which you want your OneDrive to appear -- for example, Documents. You can also choose to create a new library, and have it appear in that new library.
From now on, when you open that library, OneDrive will appear underneath it. Note that OneDrive and its files actually stay in its original location, and it continues to sync as always. In essence, by telling OneDrive to show up in Documents, you've created a shortcut to it there.
Use markup and comment enhancements
Those who use Word's markup tools for working with others will be quite pleased at some extremely useful changes to the way that you can collaborate with others on a document using Word's markup features.
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