@The Pentacle Queen,
A lot of learning for me has been cases where common sense "crystallized" in my head. I'm not sure if that expression I've been using with myself makes sense to others but what I mean by it is when experience takes common sense you already knew and gives you a much deeper understanding of it. Many times the insight I've gained is not that it is wise to do X but a better understanding of just how important it is to do X and just how often you will fail if failing to do so.
Web Development
The layperson consciously notices largely aesthetic elements of the UI (e.g. does it look pretty?) while the bulk of their experience is driven by less flashy parts of the function (does the information architecture make sense?).
So when you put function over form, remember that the guy that gives it a better paint job might get more buzz. You can get a lot of mileage out of the paint job, even if it's a superficiality to the app.
Shakespeare said it best about dress, and it applies to almost everything:
Costly thy habit as thy purse can buy, / But not express'd in fancy; rich, not gaudy; / For the apparel oft proclaims the man.
Appearance may be superficial, but it's very important to the first impression of most users.
Design
This is from a famous quote I can't remember the source for right now: Perfection is often achieved not when you can't think of anything else to add. But when you can't think of anything else to take away.
Basically, it's a "less is more" and it was a big lesson to me in design, where my natural instincts are toward "more is more". For a guy like me, when I've found I can't take any more of the minimalism I'm enforcing upon myself I'm usually got it about right.
Poker
The 5% inspiration and 95% perspiration rule.
Sometimes all the skill in the world isn't as good as discipline and patience. You can be the most skilled player on the table but consistently be the biggest loser. Sometimes the less I try to outplay people and force the action the better I will fare. Letting the game come to you is a lesson in patience and timing. The best moves you have aren't nearly as good as merely picking the best spots. Learning to wait for the right "when" is often more important than the right "how".
Logistics
Time is money, distance is money. Everyone knows this but in logistics you learn it a different way, where late can mean thousands of dollars in costs. Logistics is all about moving things around which ends up being much more complicated, and crucial, than I'd ever expected prior to becoming an impromptu logistics guy.
Marketing
Being more specific and more targeted isn't as sexy as going broad and glitzy but tends to have a much better ROI. So all the "glamor" marketing such as TV, radio, and print won't tend to do as well as something like search marketing, where you market to someone searching for exactly what you are offering.
Very few cases are good fits for general branding, and if you focus on getting your message to the few people most interested in it (as opposed to everyone you can get in front of) you'll have the best ROI.
The the next thing you learn is that scale is the enemy of ROI when it comes to marketing. So your cost per acquisition suffers if you let volume dictate your strategy, and your volume suffers if you let ROI dictate your strategy.
Picking the right spots in marketing is the lesson least learned by marketers, who often fail to marry their creativity with objective measurement. Getting the right balance and starting with ROI lets you out-finesse your competition with a lot less and marketing is direct competition sometimes.
English Teacher
You don't need to know anything about the rules of grammar to use the language, which is best done by rote (remember this when you try to learn a language). But grammar becomes important when interfacing with different languages.
Often the ESL student will understand English grammar better than native speakers.
Hiring people
You really need to be more pushy ("persistent" if you are a salesperson) than I ever want to be to be successful in sales. If you like helping others you may just be the wrong kind of person for sales. For customer service you must be much less aggressive, while as outgoing and social.
Getting the right personality types for the job makes more of a difference than anything else will tend to for sales and customer service positions. You want aggressive and outgoing for sales, passive and outgoing for customer service. For operations personality isn't as much of a king maker, but the general profile is less outgoing and social.
For sales and customer service you can actually do personality tests that will fairly accurately predict how someone will perform in specific roles. I was very surprised to find out how accurate some of the pre-employment tests could be (I have specific ones in mind, such as the "Predictive Index").