Seth Godin had a good post a couple weeks ago titled, The danger of starting at the top where he talks about the downside of selling directly to a company's CEO. They key line is this:

When making a b2b sale, the instinct is always to get into the CEO's office. If you can just get her to hear your pitch, to understand the value, to see why she should buy from or lease from or partner with or even buy you... that's the holy grail.

What do you think happens after that mythical meeting?

She asks her team.

And when the team is in the dark, you've not only blown your best shot, but you never get another chance at it.

I agree and disagree with this. Two thoughts:

Yes, you need to be careful when going straight to the top, but I don't think you need to be afraid of selling to the CEO directly. But you do need to be careful in your approach. In short, don't sell. Have a conversation. Ask about her business, what problems she has, talk about what you do, your industry, her industry, potential synergies, who would be good to talk to, etc. If you're not selling, you should be comfortable talking to anybody.
While you're having conversations, you should also be evangelizing. That is, you should be drip marketing your prospects. I defined drip marketing in earlier posts as:

Regular, short and highly interesting/engaging/insightful pieces of information (most often without an ask) that educate the recipient and — just as importantly — change their perception of what you do in a favorable way.

If you're having conversations and "dripping" the right people, you should be free to navigate your prospect's company to find the person that will be most interested in your solution.