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Why would the tribute
named Foxface just arbitrarily eat the poisonous berries that she saw Peeta picking?
She appeared well-versed in
what is edible and what isn't, and wilderness survival in general
and her last action doesn't seem like it would fit her character...
In the books it goes into detail on that. Foxface, as Katniss called her, was fast and the most intelligent by far of the Tributes. That's how she survived so long; stealing from her opponents supplies using her speed and smarts. That was also her undoing. Because Peeta gathered the berries, Foxface never assumed that they weren't safe to eat. She thought Peeta knew what he was doing since he was alive so long, not realizing that Katniss did all of their food gathering. Because she didn't second guess Peeta's knowledge, she just ate the berries, and was promptly dead.
Foxface's body was emaciated when they saw her dead in the novel. That's hard to reproduce on screen so they didn't bother.
In the book, Peeta shows Kat a handful of the berries he's picked, and Kat is examining them and remembering what her father had told her about them ("Not these, Katniss. Never these. They're nightlock. You'll be dead before they reach your stomach.") when the cannon fires. Kat fully expects to see Peeta drop dead at her side, when instead a hovercraft comes in and plucks Foxface's body out of the bushes nearby. This changed a bit in the movies; Kat hears the cannon, then finds the berries, freaking her out. Then, after Peeta's obviously not dead (by pure luck that he hadn't eaten any yet, as in the book), they find Foxface not far from where Peeta had been picking.
In either case, Foxface had survived so far mainly by staying hidden, and by raiding the Careers' stockpile from the Cornucopia, which Kat destroyed halfway through the Games. The entire time after Rue's death, when Kat was looking for Peeta, tending to him, and then after the Feast when Peeta tended to Kat, Foxface was starving to death. She may also have gotten sick from the rain, not having a proper shelter. We never know what was in her own pack at the Feast, but it was probably food, which didn't last her long enough. Seeing Peeta pick berries, and thus assuming he knew what he was doing, the temptation was just too much.
There are debates about whether or not Foxface committed suicide or that she ate the berries by accident without checking to see if they were poisonous, or even if she faked her death and fooled the Capitol.
The book makes it seem like it was an accident - nearer to the end of the games, when Katniss goes to sabotage the Careers' camp as a part of her and Rue's plan, she sees Foxface carefully making her way through the minefield to steal food. Later on, Foxface steals a little bit of Katniss and Peeta's cheese and berries, and she must have eaten the berries (Nightlock) right after stealing them, as her body was taken by the hovercraft nearby; that was when Katniss had discovered that Peeta had been picking the Nightlock.
In the movie, however, there is a scene that shows Foxface in the training center sorting out edible plants from poisonous. Because of this scene, her death looks almost like a suicide. She knows what berries will kill her, and so she must have known that the berries she had stolen were Nightlock.
Canon quotes to make clear not only that Foxface died by accident, but also to tell us (Katniss's speculation on) how this came about:
It takes a while to explain the situation to Peeta. How Foxface stole the food from the supply pile before I blew it up, how she tried to take enough to stay alive but not enough that anyone would notice it, how she wouldn't question the safety of berries we were preparing to eat ourselves.
[...]
I can't pretend I'll miss her, but I have to admire her. My guess is if they had given us some sort of test, she would have been the smartest of all the tributes. If, in fact, we had been setting a trap for her, I bet she'd have sensed it and avoided the berries. It was Peeta's own ignorance that brought her down. I've spent so much time making sure I don't underestimate my opponents that I've forgotten it's just as dangerous to overestimate them as well.
-- The Hunger Games (emphasis mine)
