In this dissertation we discuss aspects of the transitions between metastable vacua in scalar field theories. These transitions are caused by nucleation of bubbles of one vacuum in a background of another vacuum, and may have relevance in cosmology. Such processes are typically exponentially suppressed in the height and width of the barriers between the vacua. We demonstrate ¨ several scenarios where this intuition fails. We use a functional Schrodinger approach to show that tunneling of a scalar field through two barriers can be exponentially faster than tunneling through a single barrier. We determine the conditions that the effective potential must satisfy for a large enhancement in the tunneling rate to be possible. Both the tunneling rate to nearby vacua and to distant vacua in field space can be enhanced by this process. It may be possible to test this phenomenon using superfluid Helium-3. Nucleation of the B phase in samples of the supercooled A phase of superfluid Helium-3 is observed in seconds or minutes, while the characteristic decay time is calculated to be longer than the age of the universe. We propose a resolution to this discrepancy using resonant tunneling. This explanation makes the distinctive prediction that there exist multiple peaks in the nucleation probability as a function of temperature, pressure, and magnetic field. Next we investigate in detail Coleman-de Luccia tunneling. We show that there are four types of tunneling, depending on the importance of thermal and horizon effects. We estimate corrections to the Hawking-Moss tunneling rate, which can be large. Finally, the tunneling rate for a scalar field described by the Dirac-Born-Infeld action is calculated in the Hawking-Moss limit using a stochastic approach.