Is there any specific distinction between saying "he's to blame" and "he's guilty"? Would you use them interchangeably? If not, what would be the most common situation for each one?

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"guilty" is normally used in the context of someone having specifically done something wrong, and sounds a lot more serious. "to blame" just means that your actions have caused something (usually negative) to happen.

I'd say someone was to blame for maybe a car breaking down or for someone losing their phone, but "guilty" sounds bizarre in this context. "guilty" is more for specific actions like stealing or cheating (you could say 'he's guilty of taking credit for other people's work', though, so it doesn't have to be a single word), but it's frequently associated with actual crimes so it can be a bit too serious to use for minor things.