I, like you, wanted to learn Rule Machine because I had a desire to make more complex rules and I wanted to start with a simple one. It took a while, but I feel I am at the reasonably competent level now; Rule Machine doesn't eat my lunch anymore, but sometimes I see it following me home from school with a nasty look in its eye.
Seriously, let's start by looking at what you've done so far, what you expect it to do, and fix the gap between those things. You said you want the rule to work after dark and that it should be based on two different sensors and either one can set off the rule. Good so far. The rule you wrote in the OP should be turning on your Living Room Outlet whenever either the Front Door Sensor is "open", the Living Room Motion Sensor is "Active" or both. If that's not happening, you have a problem that has nothing to do with the rule.
Okay, assuming that trigger is working correctly, before you make your conditional rule for the Living Room Outlet only turning on "after dark" you have to decide how you are going to define "after dark". You could do as you've done, and set a time on it (although note that in the posted example, this rule would only work in the 30 minutes before sunset until sunset; as @neonturbo mentioned, this probably should be until sunrise. However, if you are using modes, and one of them fits your scenario appropriately, you could use that as your conditional trigger. You could also use a light level sensor to decide what "dark" is. But, you used sunset, so let's stay with that.
You want to encapsulate your action within a conditional IF-THEN statement. This way, the rule will process based on the triggering event (the motion sensor or the door sensor being activated) but the ACTION will only fire if it meets the conditions you've set. So you need to add an action in Rule Machine, but you want to choose "Conditional Action". This will give you the option of an "IF (conditions) THEN" action or a "Simple Conditional Action". What's the difference? Well, as far as I can tell (and please someone correctly), an "IF (conditions) THEN" action can be complicated, with multiple conditional levels (nested, if you so choose) and multiple actions; a "Simple Conditional Action" has one condition and one action. In your case, an "IF (conditions) THEN" might look like this:
IF (Time between Sunset-30 minutes and Sunrise(F) [FALSE]) THEN
On: Living Room Outlet
END-IF
Note that you don't need the "END-IF", but getting into the habit of it will help you when you start making more complicated rules.
The same rule, using a "Simple Condition Action" might look like this:
IF (Time between Sunset-30 minutes and Sunrise FALSE) On: Living Room Outlet
Obviously, this second version is simpler, and it is helpful to know both ways, but when you start getting into more complicated conditional triggers and multiple follow actions, allow with "ELSE" statements and the like, being adept with the "IF (conditions) THEN" action will probably aid you more.
One thing that helps immensely with using Rule Machine is that it does give you immediate feedback on whether conditional statement's conditions are met, both individually and as a whole condition. One thing that will drive you crazy is the lack of ability to cut, copy, and paste within Rule Machine.
Finally, consider turning on Logging for Events, Triggers, and Actions when trying to Debug. It will save you some headaches. One thing I do is take the log entries for when the rule did what I expected it to and the ones from where it didn't, and I compare them side by side in a text editor. That way I can find the differences and figure out what I've done wrong.
I hope this both helps and makes sense.