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Made the hour trip to the GW store nears me that sells FW models and came back withe Harridan and Heirophant. So I'm about to wash the models with soap as the instructions say to, and the brass rods for pinning I ordered should arrive tomorrow. But I'm wondering when to actually paint the titans. I was going to fully assemble them and then paint like normal. But I've seen a couple people suggest to instead paint the limbs and bodies separately and then put them together. Which should I do?

Once you have the pins in place, I recommend trying putting everything together with bluetack or similar, and try to visualize how you're going to paint every part. If you encounter hard to reach areas, that's generally a good case for separate painting before assembly. The Harridan and Hierophant are also both quite large, so doing things like painting their undersides once they're fully assembled can require custom preparation.

I left off the gargoyle from the Harridan and left the flesh hooks off my Hierophant.
Everything else is pretty easy to reach assuming you haven't attached it to the base.