"Should I switch the routers to make the R6200 the primary? Should I use LAN-WAN?"
LAN-LAN has the advantage that all the devices share the same subnet. This will allow you to share files and use printers, etc spread across the two routers. With a LAN-WAN connection, computers on the primary router will not be able to access devices connected to the secondary router. Secondary router computers can reach the primary router computers, but opening the connections tends to be much more complicated. Stick with LAN-LAN. Also, port forwarding for connections coming in from the Internet are much easier with LAN-LAN dual router networks. For example, if you have a security camera on your home network you might need port forwarding if you want to view the camera's image when you are away from home.
Unless there is a good reason for swapping the two routers over, leave them as they are.
"I have a smart tv in my living room that I currently use Wifi connection on, but I am a man and want the best picture. Should I hardwire with Ethernet powerline [adapters] from primary router?"
You can use Powerline adapters connected to either router. I use the following adapters for my TV.
http://www.tp-link.us/products/details/cat-18_TL-PA4010KIT.html
I also have an extra adapter to provide connection from my desktop PC in another part of the house. Powerline networks typically can have 6 or 7 adapters in the network.
"should I get a second modem, uncascade the two routers, keep one modem/router in the office and the other modem/router next to the tv, thus having two separate router setups?"
You can only have one modem connected to your ISP line. Connect a second modem and the connection will die with ADSL. With cable, you might be able to connect a second modem, but your ISP will charge you for two Internet connections.
"My overall plan is to build a media server from scratch to have EVERYTHING on it and be able to stream to any device, including the TV. This will allow me to get rid of blu ray player, cable and all my external hard drives. Just have one centralized media server."
The LAN-LAN set up is the best way to achieve a complete network streaming from a single media server.
"Which leads to one last question, how can I stream stuff from the server to the smart TV?"
Many smart TVs provide a streaming capability from a media server on the same subnet. For other TVs then you might be able to find a media server add-on unit that will provide the same functionality including remote control as a smart TV can provide.
As a slight tangent to this question, for many of the catch-up TV services and for services such as Netflix, I use a Chromecast dongle plugged into a HDMI port on the TV. This gets its connection to my network by WiFi, but handles full HD movies without any flicker or breaks in the stream. The TV/Chromecast is about 7 metres from my router. I use my Android smart phone, or a Windows laptop or a Chromebook laptop as the remote control for the shows via the Chromecast. There are extension apps for the Chromebook that act as a media extender. Sometimes I use either of the two laptops (above) with the TV so that the whole family can watch when I visit specific sites on the Internet.
Once set up, a Chromecast dongle can be managed from an Ethernet connected computer on the same subnet.
I hope this helps.