ePSXe is the best PSX emu hands down, and 'most' games look even better on it than on real hardware.
I shudder at all of you FFVII fanboys though. It wasn't that great of a game, the story had too many plot holes, character development was no where near as good as it could have been. It's not a bad game, but it's definitely not one of the best.
My offers for RPGs really depend on if you want good graphics or not, and how much time you are willing to devote to a single game. There are a large number of great games for older systems, and although the graphics aren't perfect, they focus on gameplay. The Star Ocean and Shin Megami Tensei games have great stories, awesome music and deep gameplay, but the graphics are greatly outdated. Chrono Trigger is another great SNES RPG. Good PC based RPGs are mostly based off DnD, like Planetscape, Baldurs Gate and Neverwinter Nights. PSX games started to focus more on FMV story development, but Chrono Cross, Xenogears, FF7/8, Tales of Destiny are a few of the deeper games.
My advice is to start with older games first, if you can get around the highly outdated graphics. No 3d models, limited resolution sprites, minimal frames of animation. But from days when games were made to be fun, instead of to just look good.
I all depends on what kind of game you want to start off with. The RPG genre is split into a number of sub-genres. Action, DnD, Strategy, and various different styles within each.
The DnD based games are incredibly deep, and usually offer a very open ended style of gameplay. It's usually non-linear except for the few key story quests that you eventually have to do to advance the game. Because of this, these games are mostly on PC, and offer players a chance to develop huge mods to change the entire game.
Most console based RPGs are much more linear, because of the limitations of the hardware, but this usually just means that the character development and overall story are deeper because it will only unfold in a predetermined manner.
SRPGs usually don't have as deep of a story as a standard RPG, but offer unparalleled play hours and customization. Fire Emblem, Shining Force, Final Fantasy Tactics, Front Mission, Tactics Ogre are all great SRPG series.
At the end of this, I'd say start with a good SNES RPG, either Star Ocean, Secret of Mana, Final Fantasy 6 or Chrono Trigger and go from there. Fire Emblem and Front Mission are also on the SNES, so you can try some moderate depth SRPGs, but nothing that will suck up 400 hours of you life getting that last elusive piece of equipment to turn your main character into a god of battle. Most of the SNES RPGs usually take from 30 to 100 hours to beat, depending on what you try to do in them, but others can easily consume a nice piece of your life(I've logged over 1500 hours into Star Ocean 2) if you try to get everything available. But just find an RPG, try it for a few hours, if you don't like it, try something else. It may take a while before you find the particular sub-genre that you enjoy.
OMG, this probably makes little sense, but I've been typing it over the last 4 hours while dealing with ComCast customers, so gimme a little slack.