Synching allows you to save your bookmarks, extensions, passwords so that, if you have to log in to another machine, everything is still there. Synching only syncs data with the account that is currently logged in. In other words, changes to your work account will not sync to your personal account.
To have information sync, you must be logged into Google Chrome properly. To learn how to do that, check out THIS ARTICLE.
To understand what Syncing is and how it works, start HERE.
To see how to turn on Sync, watch THIS.
Or, watch the whole video below!