If you need to test a circuit breaker with a multimeter and you're working in a live breaker box with 240v, what is the best safety equipment to use (eg: gloves, shoes, shield, etc)? It doesn't seem right working with those small multimeter lead handles with bare hands, but most contractors seem to have no trouble doing this. I am being overly paranoid, or is there a better way?
Most important equipment is the right multimeter.
If you're working on your panel you want
CAT III or higher.
These will typically come with anti-slip probes which will help your confidence some.
You'll want the right meter, for sure
The most important thing when probing on mains circuits is to use the correct meter, as Jason alludes to. You will want a CAT III/300V meter if you live in an apartment or flat where you don't have feeders or branch circuits that run out to lampposts, outbuildings, or such; if you do have wiring runs buried in your yard that you need to work with, you'll need to up that to CAT IV/300V. Furthermore, this rating needs to be backed up with independent testing and the provenance provided by listing and labeling; many bottom-of-the-barrel meters claim to have a CAT III rating, but don't come close to meeting the requisite IEC 61010 standards for it.
Beyond that, it's mostly a matter of going slowly and carefully, so you can think ahead of what you're doing, and thus keep your fingers away from energized bits. If you have alligator-clip attachments for your probes, a procedure of "turn power off, set up measurement, turn power back on, take measurement, turn power back off again" can be used, but may be problematic in terms of remembering what you last did with the breaker. Of course, if you're trying to test a circuit for liveness with a multimeter, you'll want to check it on a known-working circuit first to make sure it isn't going to lie and tell you the power's off when its not.
In addition to the CAT3/4 answers, I would like to add that in many cases you might not need a multi-meter.
If all you want to do is determine/test whether a circuit is live you can use a contactless voltage meter:
With one hand you hold the tester and press the tip lightly against a line wire or a screw/terminal and it will beep when live/hot. The tip is isolated, not metallic, and there is no electrical contact.
And if you need to know whether it's 120V vs 240V, and/or you want to make sure the neutral makes a circuit, e.g. at an outlet, you can use a 120/240 tester:
This device has two lights, one to indicate 120V and another to indicate 240V.
A multimeter is great for measuring the voltage and/or current -rather than determining whether the line is hot-, but comes rightfully with some concerns about safety and requires a little more carefulness, as you seem to be aware of.