You haven't got the syncs quite right. there are two fields, the 'odd; field and the 'even' field. Lines 1 to 312.5 are slightly different to lines 313.5 to 625. The half line is there to delay the second field so the lines interlace with each other. In true PAL, there are four fields because as well as the syncs, the color burst advances 90 degrees phase on each field but you probably don't want to worry too much about that.
Also don't forget that each picture line also has a blanking period consisting of a front and back porch, 11 cycles of color burst alternating in phase on each line and a sync pulse.
The higher resolution picture part is toggling one of the port pins, high = bright, low = dark. Normal PAL pictures have a video resolution reaching about 5MHz per pixel but as you only have a 20MHz clock and you need two instructions to raise and lower the pin signal and each instruction takes four clock cycles, the best you can achieve with a 20MHz clock is 2.5MHz.
I have not tried it myself but I hear that some people have managed to generate video using the UART in synchronous mode. When synchronous mode is selected, you have to provide an external UART clock which becomes the 'dot clock' to produce one pixel. Unlike async mode it doesn't add start and stop bits so you can use it as a video shift register and take the video from the TX pin.
Brian.