The earliest consumer cards I remember having commonly available TV out on were PCI Rage II, but ATI might have done some pro cards before that.
Typically however, the TV out doesn't happen unless turned on by the drivers or OS, the only cards I know will do TV out from power on are Geforce 3s with the TV out option.
However, if you really want to get into it, this site is best resource for getting older cards outputting to TV, even then BIOS may not show, and you may need certain chipsets that are capable of TV timings, Cirrus Logic ones always seemed to work for me... http://www.epanorama.net/circuits/vga2tv/cindex.html
Unicorn herding operations are proceeding, but all the totes of hens teeth and barrels of rocking horse poop give them plenty of hiding spots.