Chloroform should definitely be avoided. Its a halogenated hydrocarbon and has the expectable hepatotoxicity. Also it sensitizes the myocardium to the action of catecholamines which can lead to a sudden shock (I.e unexpected surprise) causing cardiac arrhythmias.
Ether on the other hand is much more benign. If acetaldehyde is a metabolite then it can't be produced in huge quantities, like it does when ethanol is drunk in large amounts, a few hours after drinking alcohol I can taste that horrid fruity smell of acetaldehyde on my breath, whilst after drinking or inhaling either diethyl or diisopropyl ether then it just isn't there. Can taste the ether but not acetaldehyde or propionaldehyde after inhaling or orally taking either.
I'd start with a few ml if dosing orally, ideally floated on an iced soft drink shot and with a chaser handy. It lasts a lot longer by mouth, and hits harder.
DEFINITELY no smoking around ethers, they tend to be flammable as fuck, and diethyl/diisopropyl ether are no exceptions. Also one needs to be careful in storage to make sure the fuckers don't peroxidize. Diisopropyl ether being MUCH more prone to formation of violently explosive, highly brisant and EXTREMELY sensitive alkylidene peroxides and needs testing with a drop placed on iodide-starch strips (the oxidizing nature of the peroxide oxidizes iodide ion to iodine which reacts with the starch to give the characteristic blue-black indigo colour of starch reacting with iodine. The deeper the color the more peroxide present. And if present then it needs to be treated to destroy them, then distilled, as long as no peroxides are visible as even traces of solid, then the peroxides destroyed. There are a fair number of ways to do so, and they are documented online. Also never distill ethers to dryness if they contain peroxide or else if they could conceivably have come into the presence of air during a reaction, as those little fuckers are EXTREMELY shock/friction/absence of three 'hail mary's sensitive and damn powerful explosives.
They need to be checked regularly for peroxidation as these can form in storage.
But if its a small quantity of ether, such as sufficient for a session then no need to worry, since it'll all be gone fairly quickly.
Its best done, IMO from a small bottle, into which is poured a measure of ether, similar to how an alcohol shot is measured, and then after making sure the main container of ether is elsewhere and capped, and then breathing through the nose from the bottle mouth, that way its controllable, if used by inhalation, for oral use, a few ml floated on an ice cold drink is ideal. Although another way is a cocktail I came up with, I call it the manhattan project, a pun on the US nuclear warfare R&D program and the manhattan cocktail. Its codeine linctus (ironically, and surprisingly, there is a brand in the uk that includes a little chloroform, presumably as either flavour or preservative, and it works perfectly in this. that goes on the bottom of a long glass, and carefully, lime soda is floated on top of the thick syrup, ideally with the vodka added first, not too much because ether is potent as hell, but just enough to taste in the lime soda, then a sqeeze of fresh lime, and a couple of lemon and a lime slice are used to trap a little glass containing ether on one side, cut so as to fit together in a closed gate-like pattern, two over the glass and one bridging the other two to hold the shot in place. the ether diluted with a SMALL amount of vodka, just enough to give it sufficient volume to go down the hatch and pour easily, and then downed in one. The lime/vodka blend washes down the ether then the thick codeine syrup coats the throat.