First, look at the help of Nearest, second definition:
Nearest[{Subscript[elem, 1]->Subscript[v, 1],Subscript[elem, 2]->Subscript[v, 2],[Ellipsis]},x]
gives the Subscript[v, i] corresponding to the Subscript[elem, i] to which x is nearest.
Second, I have no idea how you got a Hold to be honest.
First@*nf
is the same as (in outcome)
First[nf[#]]&
Basically applying first the nearest function, then taking the First, but it works as a single function.
First@nf /@
does not do what you want:
f@g /@ {1, 2, 3, 4}
f@*g /@ {1, 2, 3, 4}
gives:
{f[g][1], f[g][2], f[g][3], f[g][4]}
{f[g[1]], f[g[2]], f[g[3]], f[g[4]]}
Note that in the first example f is applied to g, not g[1] ! It has to do with precedence(order, ranking) of the operators.