I'm just getting ready to switch from PS CS6 & LR5 to CC and although I've used LR for several years and PS to a much lesser extent I'm very naive and not completely sure the proper way to complete the changeover. I'm particularly concerned about preserving all of my info and the connection between LR and my Zenfolio & Flickr accounts. Also, will my CS6 workspace switch over or will I need to go in and recreate it? I'm sure these are very basic questions and seem rather silly but I'm not overly computer literate and this stuff is all new to me.
For Lightroom, your publish settings for Zenfolio and Flickr are maintained with the catalog, so will follow the catalog as you migrate, including from the perpetual license to the CC license.
For Photoshop, your custom workspaces and settings can be synchronized to the cloud and copied to the new version. After you've signed in to Creative cloud, sync your setting in PS by choosing Edit > your name > upload settings (and download settings, in the new version). Note that you can have CS6 and CC installed at the same time, so don't uninstall CS6 until everything is verified and copied.
Also to be clear you will need to remove the Lightroom app and reinstall from the CC Desktop app.