That's a broad question. So, some random, first-things-that-come-to-mind tips.
1. Don't try to "finish" your world before using it to run adventures.
This depends on your DM and campaign style I suppose. But I've found sketching out the most important places, people, groups, and things and then creating and filling out the details as I created adventures worked best.
2. Watch the most recent RW GenCon Video
They have a video where they run a Pathfinder game in RW.
3. Watch the RW YouTube "Spotlight Series" (
http://forums.wolflair.com/showthread.php?t=54556). See, especially, the most recent as of this post, Week 7: "Prep and Run Enounters"
4. Put the Storyboard or Map into the Navigation Pane
For most of the time when running an adventure, you are going to be following a storyboard, or you are going to be referring to a map. RW allows you to put a map or a storyboard into the navigation pan, so you can click on the pins on the map or the nodes in the storyboard flowchart and have the associated scenes (or other topic type) appear in the mane pane in the middle. This makes it easy to navigate through your adventure.
5. Create a session-specific view
Before my game session, I put all the topics that will be most important into a session view for that session. My world is getting so big that I would otherwise need to run searches for topics and articles. If I know that there is a high likelihood that I will need something, I put it in the sessions view. A bonus to this approach is that after the session, it makes it easy to remember what I have to reveal or update. I'm not great about revealing on the fly and I like to add in-game date snippets after the fact, so that the timeline records the party's campaign history. The topics and articles in the session view become a kind of to-do for after-session updates.
6. Prepare and Test for Player View
You did not state if you play an in-person game or remote or a mixed. Things can get a little complicated if you use RW in conjunction with a VTT, video conferencing, HeroLabs, and other tools. That's outside the scope of what I think you are asking. I'm assuming a more traditional at-table experience.
For traditional, at-table play, you need nothing more than make sure you've backed up your realm and have a place to plug your computer in. But one additional bit of tech setup that I think is worth it is connecting your computer to a second screen, whether a small monitor facing the players or a large TV. I use the player view mostly to throw up maps, revealing areas as they explore. It works great for this.
It is simple to set up, so long as you know how to display to a second monitor in "extended screen" mode. Still, spend some time practicing. Even after you've run games with this set up and are comfortable, it is always good to set things up before the players arrive so you don't waste precious game time with tech setup and troubleshooting.
Not sure if these are the kinds of tips you are looking for. Am happy to write to more specific questions. I wouldn't be DMing if I had to DM without RW. I makes my life that much more easy and a DM.