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Most of the areas around Florence are punctuated by river valleys with farms and other private land, so limited hiking opportunities. And there's a lot of flatland with short steep ridges in between -- good for a few kilometers but probably ten at most. Are you in Florence the whole time? If closer to Siena, there are hundreds of trails that go back to the days of penitents walking to Rome. Or, go to San Marino, about 220 km away, for some spectacular scenery, quiet roads, and trails everywhere.
Generally, think about hikes to specific destinations. Rather than a mountain range that's known for hiking, a la the Cascades or Green Mountains, there are trails up to a major chapel or monastery or similar location. These are some of the most impressive areas to hike and trails are not particularly long and are pure hiking -- no scrambling or steeper. Views can be spectacular.
I'd avoid the east coast. It's very hard to find a route that doesn't dump you onto major coastal roads for a couple miles, and the driving on those is crazy, whether you're on a bike or on foot.
Are you open to driving a couple hours to Cinque Terre? It's best toured on foot, and it's one of the great destinations in the world. Plan on an overnight there, possibly two, but it's worth it. Some of the best hiking (and some of the best food and scenery) in Italy.
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