.pcx files are just image files, similar to .gif, .jpg, .png, etc. You just need an editing program that recognizes the format, such as Adobe Photoshop
Not quite sure what you mean here... changing any .pcx file (without changing its name) should change how it appears in the game.
Civ3 loads the .pcx files every time it runs, so if you make changes while the game is running they won't show up until you exit completely and restart civ3.
Make sure you make a copy of any .pcx file you edit in case you screw up or want to go back to the original at some point.
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