That's a hard one, because everyone has different requirements, and different rolls have different requirements too.
But in general, as a first pass you want to start by weeding out the people who don't know anything and are generally clueless at the stuff required for the position. That's pretty easy, you simply ask really easy questions and if they pass those without hesitation then they aren't clueless.
Like for example a PCB person you might ask them to name some PCB material and common thicknesses or something, or some ways to reduce EMC issues etc.
For a micro person you ask about different brands, compilers, problems they have had, do they use forums etc.
For an analog circuit designer you might ask some basic opamp stuff.
If they can answer the easy "do you know jack" stuff then I've found they inevitably know the more detailed stuff.
You might as them details about technical stuff or projects they have worked on in the Resume to see if they are bullshitting.
I generally don't like putting people on the spot with actual in-depth design questions or "solve this" puzzles, because I know that good people can get nervous in interviews and get mental blocks. So I try to ask questions that are fairly open ended so I can guide them if needed. My favourite is to give them a PCB and tell me something about it, anything. Prompting with "name some packages", or "do you recognise any devices" if required etc.
Actually, the first pass is the Resume, and some are simply immediate bin tossers based on the wording. I've found that in general you ca weed out 80% or so based on working in the resume. Formatting means jack, it's what you say and how you say it. I need to get "the vibe".
A big thing is what they have to show off. Someone who doesn't bring anything to the interview (actual hardware, photos, docs etc) generally goes to the bottom of the list, and would have to work a lot harder to impress me.
Personally I don't care too much about someones personality, but I prefer people who speak their mind, not the timid "yes sir" type. I like people who aren't afraid to talk back, speak up when they think something is wrong, and have a bit of an attitude.
They could be a chain smoking, environment hating, George Bush loving, drug addict, nuclear war mad, fundamentalist christian creationist, cat loving yank with 20 kids for all I care - if they can do the job well then they are in with a shot. I don't necessarily have to like them much as a person, or have much in common with them. I'm not hiring a friend, I'm hiring someone who can get the job done.
Passion for electronics and engineering is important. It's obvious if they have it, or if it's just a 9-5 job for them. Not a deal breaker, but it can make a difference if I have to chose between a couple of people. I'll go with the enthusiastic passionate one first.
Of course, some of that HR crap comes into it too. Like being able to fit in with the team, company culture etc. I'm very tolerant or personalities, but I know some others in the team or company are not.
Dave.