starting values

Nonlinear fitting is not guaranteed to converge to the global optimum (the solution with the smallest sum of squared residuals, SSR), and can get stuck at a local minimum. The routine has no way to determine that; it is up to you to judge whether this has happened.

fit may, and often will get "lost" if started far from a solution, where SSR is large and changing slowly as the parameters are varied, or it may reach a numerically unstable region (e.g., too large a number causing a floating point overflow) which results in an "undefined value" message or gnuplot halting.

To improve the chances of finding the global optimum, you should set the starting values at least roughly in the vicinity of the solution, e.g., within an order of magnitude, if possible. The closer your starting values are to the solution, the less chance of stopping at a false minimum. One way to find starting values is to plot data and the fitting function on the same graph and change parameter values and replot until reasonable similarity is reached. The same plot is also useful to check whether the fit found a false minimum.

Of course finding a nice-looking fit does not prove there is no "better" fit (in either a statistical sense, characterized by an improved goodness-of-fit criterion, or a physical sense, with a solution more consistent with the model.) Depending on the problem, it may be desirable to fit with various sets of starting values, covering a reasonable range for each parameter.