Umm, skinning and making /editing unit cards are two different things - which can need different software.
Skinning is changing the appearance of the texture file which 'clothes' the model you see in the game in the battle map. Those files are saved as .tga.dds files and a special plug-in from nvidia or a converter is needed to access them. PhotoShop, PhotoShop Elements, GIMP (which is freeware), and I think later versions of PaintShopPro should be able to use the plug-in (not 100% sure on PaintShopPro as my old version definitely doesn't).
There is a guide to skinning with PhotoShop here:
https://forums.totalwar.org/vb/showthread.php?t=66957
most of that will apply to PS Elements as well which is cheaper version. Elements has a replace colour function which is quite handy for doing quick bodge jobs to change colours of bits of skins without losing existing textures.
GIMP is meant to be quite good (and obviously free is good, LOL) but I haven't used it so can't advise.
The unit cards (the small icons you see at the bottom of the battle menu - in recruit queues etc) have to be changed separately. They are normal .tga files so are easier to find an editor for. You can just manually paint over the bits of 'wrong' colour, or depending on program try replace colour and various shadowing options to maintain shape. The 'proper' way of doing unit cards is to make a render from the 3d model using the new skin, but the software normally used for that is 3Dmax which costs about £3000, there was a free 3d program which might be able to do that (but not make new model for game) I'm not sure if it's still around - perhaps someone else could advise on that.
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