IF the game didn't force me to run around with fricking pistols for the first week of gameplay or so
I usually end up with Mini-14s, and short to mid range rifles like SPAS or AKSU by the end of day 1, and sometimes even a laser pointer and a scope. Enemy encounters on the road provide great resources. Especially Alma as mentioned.
I also hire from MERC for transporting items. I move MERC mercs around all the time to pick up items dropped in encounters and sectors, and stockpile all items in a few sectors. This way, new mercs I hire will get immediate access to everything they might need, and everything else I don't need becomes quick cash soon enough.
I wouldn't say all the NPCs suck- ones I like so far (in terms of voice acting): Bull, Steroid, Gasket. Ones I don't like: the rest I have come across. Especially Ira- I'd almost get her purposely killed if she weren't so useful for training militia.
I like Steroid's lines. "Evil Peoples!". He really shines when you have "commies" (Ivan or Igor, or worse, both of them) on the same squad.
I love Reaper. He has a sick and disturbed air about him, with intricate lines. I especially like his line when a sector is cleared. He's about the only top-of-the-line merc with pleasing lines. I can't remember all of them now, but most other star mercs sound just cocky or cheesy.
Buns is also kind of cute, I like her Eureopan accent and her choice of words. What's nicer, I like how Buns despise Reaper. You gotta try having the two on the same squad. Buns also gets into a female clash with Fox, and I think she might be racist. I remember her complaining whenever I hired a black Merc (Magic, Blood, Ice).
Ira indeed is terribly annoying. I hate her voice when she says "The army! I knew they'd sooner or later show up!". Damn fucking bitch.
For real laughing material, try hiring from MERC. They got such a weirdos with bizarre speech, especially the moronic duo that's Razor and Haywire.
For extras, trying hiring the complete MERC line up, and don't bother yourself with trying to keep them alive.