How do people commit suicide

If I understand it properly, I think there's a problem in the question itself. As you said:

The merchants give you Scroll Fragments for white items, so we can sort of divine that that is the base item value. But it doesn't really flow well from there [...]

It doesn't add up, indeed, and you gave the exact reason in your own question:

• Path of Exile has done away with a single unified currency entirely. Exact
• [...] there's no way to tell what anything is worth, or which items are worth more as part of the local economy. More or less correct

Actually, while there isn't any curve to express the value of the items in terms of value, we probably could figure one out based on the difficulty to obtain the item from the vendors.

• You can get a Scroll Fragment with pretty much any crap item (which are easy to find).
• You can make a Scroll of Wisdom with 5 Scroll Fragments (which are easy to find, but you need 5 of those).
• You can get a Portal Scroll with Scroll Fragments (but you need 15 of those). It's getting harder to obtain, but still feasible.
• You can get an Armorer's Scrap with an piece of armour with a 20% quality, or with several pieces of armor with a total of 40% quality: feasible, but you'll need patience.
• You can get a Chromatic Orb with any item that has 3 sockets of different colors and linked together: you'll have to be very patient to find one of these.
• You can get an Orb of Chance with 2 rare items that share the exact same name: it's getting super hard.
• Etc.

With that in mind, the whole currency thing becomes a matter of recipes, and the "value" of each currency item is determined by its difficulty to be "cooked" (let's put it this way) and, therefore, its rarity.

The vendor recipe system allows the player to sell items to any town vendor in exchange for a multitude of currency items and equipment. Each recipe requires semi-specific items or combinations of items be put into the sell window at the same time, and the outcome will change based on any recipes that have been matched.

Source and list of known recipes: http://pathofexile.gamepedia.com/Vendor_recipe_system

The only remaining uncertainty in this system is the drop rate of each currency item (because, of course, it's also possible to obtain them by killing mobs). But I couldn't find any information about it.

The dev diary given by Gnoupi is also an excellent reading: Dev Diary: Rethinking Gold as a Currency.

The loot system of Path of Exile is not bound at all to your character.

This is due to the fact that, technically seen, all characters can do everything, only depending on how you spend your skill points. The only real differences between character classes are starting point in the skill map, starting stats, and quest rewards.

Since the game can not possibly know how you want to play or develop the character, dropping loot for the character would be pointless.

The loot in Path of Exile might seem disappointing at first when coming from other RPGs, but in fact it is just different. Your main priority should be collecting the so called 'currency' items, like stones, orbs, shards, etc. If you don't get fitting drops for your character, you will have to take a cheap item and upgrade it to your needs.

For example, you could get a white lvl 16 weapon drop, and instantly make it a rare (yellow) weapon by applying an Orb of Alchemy. This way you can gear up much more targeted than waiting for fitting drops.

On the other hand, spending currency items at low levels is mostly wasted in softcore, as you will still level up fast and make you current gear useless in the near future.

The only real way to improve the loot you find is by modifiers on your gear, some can apply bonuses for loot quality.