A little more to add on to what Ebo said-
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1. Anyway to enlarge the size of the pen tool? Seems to be only one size when drawing lines.
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Are you talking the pen tool for making vectored lines? If so, it doesn't have a size. It's a selection device. You can fill or erase and makes masks with it, or you can "stroke" it with whatever brush size you'd like. The pen tool isn't the end result, just the way to get to the end result.
Of course, if you are talking about one of the painting tools, brush or pencil, or the eraser, or anything like that, what Ebo says is what you need. You can also open the brush pallet and it has a selection of brushes, fuzzy, hard edged, etc. You can add many more brushes that come with Photoshop too, there are more than the default.
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2. How can I tell where a layer is when I select it? Say I select a specific weathering on a skin. How can I get PS to show me exactly where its located?
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Make sure you've got your layer window open. It's a good idea to get used to navigating around all those layers and learning different ways to arrange them.
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3. I can only paint in circles? No squares?
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The Pencil tool does squares too, load up the pencil and look at your brush pallet
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4. What the hell is all the advanced blending? Talk about having me by the nuts!
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Huh? Don't know that, I do what I'd call advanced blending but I've never seen anything in Photoshop called that. Elaborate please.
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5. How to replace color?
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Again, what Ebo says, do you mean replacing colors on a file, or replacing colors on your color selection pallet, or in your swatch menu...or... ???
Ebo has Q:6 nailed down

If you want version and platform specific info, open the Photoshop help menu and type in "load brushes"
OH BOY, are you gonna have fun!!!