ESP32-PICO-D4 can it work raw?
The manual has 2 schematics. &quot;6. Schematics&quot; and &quot;7. Peripheral Schematics&quot;. Which one of those 2 is the one I need to &quot;copy&quot; ? ( espressif.com/sites/default/files/documentation/… )

I'm afraid neither. Understanding what you're doing and placing the parts that need to be close to the IC itself on the PCB you're designing, and then making an application-reasonable decision what to not include is what you'll have to do – but we don't know what you'll do, so we can't really tell you. We've already told you what's rather universally true: Decoupling capacitors need to be very close to the IC, and pull-ups will be necessary, anyway.
In every case, you can't try to route a 2.4 GHz antenna signal through pin headers. That's not how that works: It needs to be transported to an antenna using a transmission line, which in this case means a specific trace of a specific shape. If you want to connect an external antenna, you'll have to (properly) add a coax connector. If you want to place a chip or PCB antenna, you'd have to do that on the same PCB.
Honestly, you're a bit out of your depth here - that's OK.
Espressif has interest that people who didn't study this have a chance of designing working hardware, so they have written section 9:

&quot;9.1 Must-Read Documents&quot; and
&quot;9.2 Must-Have Resources&quot;.

Guess what? What you're asking here is covered in 9.1, must-read documents. Go ahead and read them!
Also, what you're trying to build sounds like one of the very many ESP32 modules that you can already buy everywhere that incorporate the necessary supply decoupling, antenna, and a bit of necessary passives on a cheap PCB. I really think you're trying to use the wrong device - this is for product designers who need to add bluetooth and wifi to a very small device, but know how to do RF design and how to deal with these kinds of ICs. You're far less space-constrained (look how gigantic your pin headers are compared to the IC...), but very much not the one integrating this IC in a complex but tiny board. Go with the existing ESP32 modules I've mentioned.