I am completely clueless when it comes to spices

if i want to cook something i haven't done before or change up the flavor of something i have cooked before, i usually start with a google search. see what others have done, read a bunch of different recipes, determine what sounds good to me, and then:

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just experimenting and practice?

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so, it is informed experimentation. i look at what others have done, use that as a starting point, but then adapt to my tastes.

for BBQ rubs, I use Amazing Ribs quite a bit (he has rub recipes for all kinds of meat). i've adjusted most of his rub recipes over the years but they are a solid start. for example, i've added more heat and reduced to salt content for many of his recipes.

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When I watch cooking shows, sometimes the chefs use this 20 spice combination to season a pork butt. When I see this I wonder how many pork butts it took to get to this recipe. I guess I'll have to practice.

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yeah, it really is just trial and error. a lot of rub recipes have a similar ingredients: brown sugar, salt, pepper, paprika, chili power, garlic powder, onion powder etc. but the major difference will be the proportions. when i started, i just picked one that sounded good and then adjusted.

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if i want to cook something i haven't done before or change up the flavor of something i have cooked before, i usually start with a google search. see what others have done, read a bunch of different recipes, determine what sounds good to me, and then:
so, it is informed experimentation. i look at what others have done, use that as a starting point, but then adapt to my tastes

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Exactly. I think for many in S. Louisiana, using Tony's as a catch all seasoning is very common. As the years pass, I continually try to educate myself on flavor combinations and put the Tony's can to the back of the spice rack. Takes a lot of money and not so satisfactory attempts, has for me at least, and I consider myself an above average home cook. Google is your friend and a good starting point.
Go to Red Stick Spice in BR. Talk to the guy or gal about things you like to cook and different spice combos that people use on particular meats.

Boneless chicken breast

Years back trying to eat a little healthier.
I would often just pan saute chicken breast in a little oil.
Always experimenting with differant spices on these taught me what I liked and what I didn't.
I also experimentmented with making a lot of differant sauces as well at the same time.
I learned a great deal doing these meals.
Quick, easy, healthy and if you screw it up, it was not a big deal.

A suggestion for you to do first before experimenting too much. Take your collection and place it on the counter, taste each and every one that is there by themselves. This will teach you exactly what each tastes like as a stand alone item, which will in turn with a bit of practice teach your brain and taste buds what they do/will do in combination with each other. Thirteen years ago I had a black guy walk up to me with a sample of some homemade (St. Croix) mango chutney to sample. I placed that spoon in my mouth, smiled at the man, and said "give me some pig". I learned what goes in it on the interweb, and it is simple shite, but pig is what it is meant to be on. Teach, train your tongue to what spices do or don't do both as a rule and for you first.