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This concept varies in degrees depending on what kind of customization you are making. For example, in the case of Peachy, whose rump is prominently displayed to the right, you have no fears. She has no more symbol and there are no marks on her body so you don't have to worry about taking them off. Peachy is a perfect candidate for a pony who is only changing symbols and perhaps hair, however despite this fact, it is important to remove symbols for ponies you intend to paint over and marks as well.
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Sweet Stuff is a pony with no marks (like Peachy) but still with a symbol (unlike Peachy) It is important to remove the symbol when doing a custom because if not it will look weird when you paint a new symbol on. ^_^ Also, if you are doing an entire body color change, when using a light colored paint it may show through unless you put several coats on which makes it very thick and uses unnecessary time and paint. Therefore, the symbol must be removed. This can be accomplished using nail polish remover (acetone based), or just acetone, Kleenex and a cotton swab (Q-tip). Take the Kleenex, fold it into about a 2-inch square and saturate this with acetone so that it is wet but not drippy. Put the pony on her side and lay this on the symbol. Let it sit for a minute to help soften the paint and then use it to wipe off the symbol use a new Kleenex and Q-tips to quickly remove any paint residue. Sometimes paint stains the vinyl on the spot where it originally was painted or can stain the surrounding vinyl when you are removing it. This is why it is important to try to be fast an efficient in your paint removal. If you are planning on leaving the pony her natural color, having the surrounding vinyl stained would not be good. Frequent changings of Q-tip (Kleenex, cottonball . . . ) and re-application of acetone will help you to avoid staining.
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Finally, if you have a pony with marks, you can try to remove them. Not all marks are removable; the one shown on Tropical Breeze's rump here is not removable but it's just a visual aide ^_^ You want to remove marks for the same reason as symbols, they won't raise an outline in the final paint job, but if you are using a light paint, the dark ones may show through and you would have to do several extra coats of paint to hide them. The marks that can come off are removed by the same method of acetone and a Q-tip. It is also important to wash your pony before you customize. Paint sticks better and longer to clean surfaces and so this is an important step. I like to use Soft Scrub with Bleach (for mild abrasiveness with a toothbrush), but any cleaning agent will probably work. :)