There is a cardinal rule in photography that newbies don't understand yet (and I was just as guilty): Direct sunlight on someone's face is a big no-no. Eventually you learn to place someone with the sun hitting the back of your subjects' heads. After that you learn to use a reflector board (white art board from the hobby store is great and flat and isn't a pain to find the sweet spot like you do with those floppy reflector discs) to reflect that sunshine back on their face because it's diffusing (reducing the harshness) direct sunlight. Beyond reflecting sunlight you can get even more dramatic results with lighting a face with a flash or strobe diffused through a soft box but that's another discussion.
But having said all that, rules are made to be broken in the right circumstance. With Jen, I broke the rule on this pic. I noticed the quality of the sun where we were and that it was just a nice quality - it wasn't overcast but it is February so perhaps the sunlight was softer due to it's position due to the season? I don't know. It wasn't the golden hour either - more like 2pm.
My point is that as a photographer you should pay attention to everything and in this case I felt the conditions were right to use the sun as my key light and I could see that her face could handle this direct sunlight (there is no rule here either - I've seen people in person and thought about how their face may take my lighting and been surprised both ways either how their face took my lighting and on the other hand how someone's face did not take the light).
I don't have a light meter. There is a meter inside the viewfinder but I find those readings don't give me the results I want sometimes so I typically start with the readings and the adjust shutter and f/stop to get what I really like. It's trial and error usually.
The next image of Jen shows how I've am using the sun as a rim light. The sun is camera right slightly behind her head and you can see that on her hair. My assistant had a beauty dish camera left with just a 30 degree grid pointed toward her face. I could have used a reflector board for fill on her face but I wanted to have a bit of an urban feel and since we were using the chain link fence the beauty dish would give the whole image just the right look.