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Here is a Atlantica Online guide about titles. I think it's helpful to have as many places as possible.
The first four sets of titles are ones you can get from one of the women outside of Athens by doing quests - there are four of them. You can only do one quest from each woman at a time (for a total of four title quests going at once, one from each woman). When you finish a quest for them, you must go back and turn in the quest, at which point they will give you an item (it looks like an envelope). You have to right-click on and use the item and you will now be able to use that title.
The easiest way to get to these women if you're over level 20 but don't have the Athen's teleport information is to teleport to Rome using the button on the right of your screen that looks like an arch, then walk outside Rome and go to Athens. If you're under 20, you'll have to walk there. You can auto-walk to any of the four women by opening up the quest log and selecting them at the top of the log (Pandora, Klieo, Calliope, or Thalia) and then clicking on 'Auto-move to NPC'. Be careful - you may run into mobs so take care when auto-walking! They're located at approximately (you'll have to move around a little, especially for Pandora) X:2090 Y:1104.
The last set of titles are only available by getting more fame points through Free League. The top few ranks are limited by a certain number of people who can have that title.
To choose your title, go to My Info -> Character and choose your title from the drop down menu of titles. You can switch your titles at any time, and it does not cost anything to do so. You start each day with no title selected - this is due to the buffs, see below.
Most titles give some sort of buff for a certain period of time. To activate the buff, simply go to My Info -> Character and choose your title as above. Your buff will instantly start for the specified period of time. You can only use the buff once per day, resetting at 6 AM PST. You cannot choose a title without activating the buff. However, if you've already used the buff for that day, you can still choose the title - it just won't give you the buff. When a buff is up, you will get a notice across your screen indicating this fact. You will still have that title selected and displayed until you change it. If you log out or dc while buffed, you will lose the buff. Buffs do not apply during Free League or Challenges. Free League titles do not add any buffs.