There are several methods to straightening a wig. First, there's the occasional wig you can use heated styling tools on (mostly the ones sold as heat-resistant, of course) but most wigs will simply fry and crimp up the minute you touch a flat iron or curling iron to them. I know this from experience, despite people telling me otherwise. Maybe I just have bad luck. Second, if you're adventurous you can use a hairdryer and brush. However, there is a very close margin on how hot you can get a wig with a hairdryer before it frizzes into oblivion, and it's hard to determine at times. This can be somewhat avoided by keeping a spray bottle of water near you and periodically spraying the wig to keep it damp, but sometimes it seems to happen despite best efforts. Obviously heat-resistant wigs are less prone to this.
Finally, there's the two methods I have used: hot water and steam. I personally prefer steam because it is easier to control and less messy, so I will mostly focus on that. For the hot water method, just get a pot of water to a boil and either dunk the wig in it, or pour the water over it. Dunking works best for things like extensions you can grab in your hand, pouring works best for entire wigs (on a wig head). Either way, you will then have a hot, drippy mess you need to put somewhere, as well as a place to pour boiling water. Be careful pouring boiling water into bathroom fixtures as they can break, definitely don't ever do it over a toilet as it could crack the porcelain. Tubs are usually ok. Let the wig drip dry in a place where it can hang freely and you should be good to go, but may need to repeat if it didn't straighten completely.
Steaming, on the other hand, is a process that takes a little bit longer but has more...interactive, I suppose, results. First though, you need a steamer. You can get a small travel-size one for a reasonable price with the downside that with very long wigs or extensively curly wigs you will most likely need to stop, refill, and let it boil once again, periodically; or you can invest a larger garment steamer that will hold much more with the added benefit of having other purposes such steaming fabric, these tend to be in the $30-150 range depending on how big and/or fancy you want to be. I have a Shark EuroPro that I think cost $40 or so. The other key item is a detangling comb, as they run freely through the wig without too much grab and pull, a brush or fine-toothed comb could snag and break the heated (and therefore more fragile) fibers. Comb the wig out beforehand to get out any tangles and to break up the curls a bit on a curly wig.
In this example, I used a sky blue afro wig. I was a bit desperate for a wig in this color and after getting several that weren't quite the right shade (was trying to match existing extensions) I happened to find this one in a store. Right color, but toooooooootally wrong style. Having steamed wigs straight before I figured I'd give it a shot, though.
First, section off the hair, at the very least section off the crown of the wig from the rest below, but with really curly wigs it helps to section it again at the middle.
Then, slowly work your way around the wig, running the steamer head down the hair from the root to the tip, following with a gentle pass of the comb. If the wig is being particularly problematic, you can try running the comb and steamer down the hair at the same time, or applying gentle pressure by holding the tips of the hair taut so that the hair is pulled straight as you steam it., but don't tug too hard or roughly drag a comb through it as it can actually cause crimping in the fiber from stretching it while it is hot. If you've pinned parts of the wig you are steaming, pull the pins out as you steam the areas they are in as they will leave creases marks in the wig otherwise. I start a few inches away from the wig with the steamer and gradually get closer, with most wigs I have been able to actually rest the steamer head against the hair and pull downwards by the end, flattening it very quickly, but I'm always careful because it is still possible to fry some wigs with steam...just a lot harder than with heated tools.
That's basically it. Once you're all done allow the wig to cool and dry before you do anything else to it as when the fiber is still warm it is flexible and will take new shapes. If there are any spot areas, a stray wave or crease you can always spot steam that once spot.
In the case of extremely curly wigs, like this afro wig, I needed to go in and trim the very ends of the hair in a few places as the curls left rough split-end-like tangles in spots.
Here are some other before-and-afters:
Also cut bangs into this for a friend's Athena Asamiya (Psycho Soldier vers.) wig. That then got lost in the mail before she got it. Ah, well. Color is Cyclamen from Amphigory (don't remember which wig it was), which is an uncommon and unusual color but pretty much perfect for that character.
Was going to use this for an Oshino Meme (Bakemonogatari) costume until I realized the hair wasn't quite long enough and a bit too dark, and ended up getting another wig. And then not doing the costume anyway.
Now while this may seem magical and all, the overall fiber quality and type needs to be taken into consideration. Many curly wigs, especially shorter ones and those with smaller and/or tight curls, and most definitely the lower cost "costume" ones, are not really intended to be straightened and have coarser, or at the very least less "silky" fiber. Possibly by design, as coarser fibers would hold curls or a set-in style better, possibly for cost cutting, but the point is that some wigs will just not have the same flowing quality as a normal straight wig once they are down. Longer wavy wigs tend to be fine though, and you can usually gauge it just by feeling the wig hair with your fingers. The straightened afro above definitely had a slightly stiff feel to it in the end but I didn't mind as it was going to be spiked and mussed up and some coarseness is beneficial to that.
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