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Trying to deface Ramon's portrait is one of the stranger requests in the Resident Evil 4 Remake—up there with trying to locate a Gold Egg and retrieving a jewel from a thieving crow's nest. Then again, if anyone deserves to have their likeness destroyed, it's most definitely that uppity zombie-child, Salazar.
You can try shooting the painting, slashing the painting, or even throwing a grenade, but it won't complete the request unless you hurl the right object. Here's where to find Salazar's painting, when you can access it, plus what you need to do to give it a nice thorough defacing.
How to deface Salazar's portrait
You can find Salazar's Portrait in the Throne Room after you've emerged from underground during chapter twelve. The Disgrace of the Salazar Family request that asks you to deface it is on the wall near the Merchant by the gondola leading to the Clocktower. It's pretty simple to get back to the Throne Room; you just need to unlock the double doors to get back to the previous area, then head to where Salazar dropped you down the hole into the basement.
Once you arrive at the Throne Room you can yono all app find Ramon's portrait to the left of the throne. Defacing the portrait isn't as simple as shooting it with a gun, slashing with your yono all app knife, or blowing it up. What you'll have to do is throw an egg at the painting. This is presumably why there are a couple of chickens hanging out in the Throne Room. Just wait for one of the birds to lay an egg, equip it in your attache case, then aim and hurl it like a grenade at the painting. If you want to get really fancy, the Square Lock Box on the opposite wall contains a Gold Egg that you could throw—a fancy egg for a fancy boi.